TW201414018A - Phosphor layer attaching kit, optical semiconductor element-phosphor layer attaching body, and optical semiconductor device - Google Patents

Abstract

A phosphor layer attaching kit includes a phosphor layer and a silicone pressure-sensitive adhesion composition for attaching the phosphor layer to an optical semiconductor element or an optical semiconductor element package. A percentage of the peel strength of the silicone pressure-sensitive adhesion composition is 30 % or more.

Description

Phosphor layer adhesive set, optical semiconductor element-phosphor layer adhesive and optical semiconductor device

The present invention relates to a phosphor layer adhesive set, an optical semiconductor element-phosphor layer adhesive body, and an optical semiconductor device, and more particularly to a method for bonding a phosphor layer to an optical semiconductor element or an optical semiconductor element package. The phosphor layer adhesive set, the optical semiconductor element-the phosphor layer adhesive body, and the optical semiconductor device.

An optical semiconductor device such as a light-emitting diode device (hereinafter simply referred to as an LED device) or a laser diode irradiation device (hereinafter simply referred to as an LD irradiation device) includes, for example, a light emitting diode (LED) or a laser diode An optical semiconductor element such as a polar body (LD) or a phosphor layer disposed on the optical semiconductor element. The optical semiconductor device emits white light from the optical semiconductor element and emits light by, for example, blue light transmitted through the phosphor layer and yellow light mixed by wavelength conversion of a part of the blue light in the phosphor layer.

As such an optical semiconductor device, an LED package including an LED package in which an LED is sealed with a transparent sealing material and a fluorescent tape laminated on the upper surface thereof has been proposed (for example, refer to the specification of U.S. Patent No. 7,294,861).

The fluorescent tape of the specification of U.S. Patent No. 7,294,861 includes a phosphor layer and an acrylic pressure-sensitive adhesive layer comprising a (meth)acrylate-based pressure-sensitive adhesive laminated on the back surface thereof, and a phosphor layer Adhered to the surface of the LED package via an acrylic pressure-sensitive adhesive layer.

However, the fluorescent tape is liable to become high temperature with the light emission of the LED. As a result, the fluorescent tape of the specification of the U.S. Patent No. 7,294,861 has a high temperature (for example, a high temperature including 75 ° C) and a normal temperature (25). °C) The adhesion is significantly lower than the adverse conditions.

Further, if the fluorescent tape of the specification of U.S. Patent No. 7,294,861 is used for a long period of time at a high temperature, deterioration occurs, and thus the brightness of the LED device is lowered.

An object of the present invention is to provide a phosphor layer adhesive set, an optical semiconductor element-phosphor layer adhesive, and an optical semiconductor device which are excellent in heat resistance and durability.

The phosphor layer adhesive set of the present invention is characterized by comprising a phosphor layer and a polyoxygen adhesive composition for adhering the phosphor layer to an optical semiconductor element or an optical semiconductor element package, and the above-mentioned poly The percentage of the following peel strength of the silicone adhesive composition is 30% or more.

The percentage of peel strength = [(peel strength under the environment of 75 deg.] C PS _{75 ℃)} / (peel strength under the environment of 25 deg.] C PS _{25 ℃)]} × 100

Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above-mentioned phosphor layer, and then at a temperature of 75 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Peel strength at _{25 ° C.} PS _{25 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above phosphor layer, and then at a temperature of 25 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Further, in the phosphor layer adhesive kit of the present invention, the polyoxyxylene adhesive composition is preferably a polyfluorene pressure-sensitive adhesive composition.

Further, in the phosphor layer adhesive set of the present invention, the polyoxyxylene adhesive composition is suitably a thermoplastic and thermosetting adhesive which is both thermoplastic and thermosetting. combination.

Further, the optical semiconductor element-phosphor layer adhesive of the present invention is characterized by comprising: an optical semiconductor element; and a fluorescent adhesive sheet comprising a phosphor layer and a layer for bonding the phosphor layer to the optical semiconductor a phosphor layer adhesive set of the polyoxo adhesive composition on the device, wherein the phosphor layer is adhered to the optical semiconductor element via the polyoxygen adhesive composition; and the polyoxygen The percentage of the following peel strength of the adhesive composition is 30% or more.

Percentage of peel strength = [(peel strength PS _{75 ° C in 75 °} C environment) / (peel strength PS _{25 ° C in} 25 ° C environment)] × 100

Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above-mentioned phosphor layer, and then at a temperature of 75 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Peel strength at _{25 ° C.} PS _{25 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above phosphor layer, and then at a temperature of 25 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Moreover, the optical semiconductor device of the present invention includes: a substrate; an optical semiconductor element mounted on the substrate; and a fluorescent adhesive sheet comprising a phosphor layer and a layer for bonding the phosphor layer to the a phosphor layer adhesive set of the polyoxynitride adhesive composition on the optical semiconductor element, wherein the phosphor layer is adhered to the optical semiconductor element via the polyoxygen adhesive composition; and the above-mentioned poly The percentage of the following peel strength of the silicone adhesive composition is 30% or more.

Percentage of peel strength = [(peel strength PS _{75 ° C in 75 °} C environment) / (peel strength PS _{25 ° C in} 25 ° C environment)] × 100

Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above-mentioned phosphor layer, and then at a temperature of 75 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Peel strength at _{25 ° C.} PS _{25 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above phosphor layer, and then at a temperature of 25 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Moreover, the optical semiconductor device of the present invention includes an optical semiconductor package including a substrate, an optical semiconductor element mounted on the substrate, and a thickness direction of the substrate and projection in the thickness direction. a reflector disposed to surround the optical semiconductor element, and a sealing layer filled in the reflector to seal the optical semiconductor element; and a fluorescent adhesive sheet comprising a phosphor layer and a fluorescent layer The phosphor layer is adhered to the phosphor layer adhesive set of the polyoxygen adhesive composition on the optical semiconductor device package, and the phosphor layer is adhered to the light via the polyoxygen adhesive composition. The semiconductor package has one side in the thickness direction; and the polyether oxide adhesive composition has a percentage of the following peel strength of 30% or more.

Percentage of peel strength = [(peel strength PS _{75 ° C in 75 °} C environment) / (peel strength PS _{25 ° C in} 25 ° C environment)] × 100

Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above-mentioned phosphor layer, and then at a temperature of 75 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

Peel strength at _{25 ° C.} PS _{25 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above phosphor layer, and then at a temperature of 25 ° C The peeling strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min.

In the phosphor layer adhesive set of the present invention, the percentage of peeling strength of the polyoxygen adhesive composition for adhering the phosphor layer to the optical semiconductor element or the optical semiconductor element package is 30% or more, Therefore, it is excellent in heat resistance and durability.

Therefore, the optical semiconductor element-phosphor layer adhesive and the optical semiconductor device of the present invention can ensure excellent light-emitting reliability for a long period of time.

1‧‧‧LED-phosphor layer adhesion

2‧‧‧LED

3‧‧‧Fluorescent layer

4‧‧‧Polyoxygen adhesive layer

4'‧‧‧Polyoxide-sensitive adhesive composition film

5‧‧‧Substrate

6‧‧‧Fluorescent patch

7‧‧‧LED device

8‧‧‧1st sealing layer

9‧‧‧Polyoxygenated body

10‧‧‧LED package

11‧‧‧ reflector

12‧‧‧2nd sealing layer

15‧‧‧Hot board

Fig. 1 is a cross-sectional view showing an LED-phosphor layer adhesive obtained by using one embodiment of the phosphor layer adhesive set of the present invention.

2 is a step view showing a method of manufacturing the LED-phosphor layer adhesive body shown in FIG. 1. FIG. 2(a) shows a step of preparing a phosphor layer, and FIG. 2(b) shows a layer of polyoxygen on a phosphor layer. The step of adhering the adhesive layer, and FIG. 2(c) shows the step of bonding the phosphor layer to the LED.

3 is a step diagram of a method of manufacturing the LED-phosphor layer adhesive body shown in FIG. 1, FIG. 3(a) shows a step of preparing an LED, and FIG. 3(b) shows a layer of a polysilicon oxide adhesive layer laminated on the LED. The step of Fig. 3(c) shows the step of bonding the LED to the phosphor layer.

4 is a step diagram of a method of manufacturing an LED device using the LED-phosphor layer adhesive shown in FIG. 1, and FIG. 4(a) shows a step of separately preparing a substrate and an LED-phosphor layer adhesive, FIG. 4(b) The step of mounting the LED of the LED-phosphor layer paste on the substrate.

5 is a step diagram of a method of manufacturing an LED device using an LED-phosphor layer adhesive of another embodiment, and FIG. 5(a) shows a step of separately preparing a substrate and an LED-phosphor layer adhesive, FIG. 5(b) The step of mounting the LED of the LED-phosphor layer paste on the substrate.

6 is a process diagram of another embodiment of a method of manufacturing an LED device, Fig. 6(a) shows the steps of preparing the LED substrate and the fluorescent adhesive sheet, and Fig. 6(b) shows the step of bonding the fluorescent adhesive sheet to the LED to form the LED-phosphor layer adhesive.

7 is a step diagram showing another embodiment of a method of manufacturing an LED device, wherein FIG. 7(a) shows a step of preparing a substrate on which an LED is mounted and a fluorescent adhesive sheet, and FIG. 7(b) shows a step of attaching a fluorescent adhesive sheet to the fluorescent adhesive sheet. On the LED, the steps of making the LED-phosphor layer paste.

8 is a step diagram of another embodiment of a method of manufacturing an LED device, wherein FIG. 8(a) shows a step of preparing an LED package and a fluorescent adhesive sheet, and FIG. 8(b) shows a step of attaching a fluorescent adhesive sheet to an LED package. Physical steps.

Fig. 9 is a view showing a step of another embodiment of a method of manufacturing an LED device, and Fig. 9(a) shows a step of preparing an LED package and a phosphor layer in which a polyoxygen adhesive layer is laminated, and Fig. 9(b) shows The step of adhering the phosphor layer to the LED package via the polyoxycarbide adhesive layer.

<Silver Body Adhesive Set>

The phosphor layer adhesive set of the present invention comprises a phosphor layer (refer to symbol 3 in FIG. 2 below) and an LED for adhering the phosphor layer to the optical semiconductor element (refer to symbol 2 in FIG. 2 below). Or a polyoxygen oxide adhesive composition on an LED package (see reference numeral 10 in FIG. 8 below) as an optical semiconductor element package. The phosphor layer of the phosphor layer adhesive set and the polyoxygen oxide adhesive composition are simultaneously or separately distributed, sold, and used simultaneously. When the phosphor layer is used to adhere the set, for example, a polysilicon adhesive composition is laminated on the phosphor layer, and the phosphor layer is adhered to the LED or the LED package via the polyoxygen adhesive composition. Or layering a polyoxymethylene adhesive composition on the LED or LED package, and thereafter, adhering the phosphor layer to the LED via the polyoxygen adhesive composition Or on the LED package.

The phosphor layer is, for example, a wavelength conversion layer (phosphor sheet) that converts a portion of the blue light emitted from the LED into yellow light. Further, depending on the application and purpose, the phosphor layer may convert a part of blue light into red light in addition to the above-described wavelength conversion. The phosphor layer is formed into a plate shape or a sheet shape. The phosphor layer is formed, for example, as a phosphor ceramic plate from a ceramic of a phosphor, or as a phosphor resin sheet from a phosphor resin composition containing a phosphor and a resin.

The phosphor absorbs part or all of the light having a wavelength of 350 to 480 nm as excitation light and excites it, and emits fluorescence having a wavelength longer than the excitation light, for example, 500 to 650 nm. Specifically, examples of the phosphor include a yellow phosphor. Examples of such a phosphor include a phosphor doped with a metal atom such as cerium (Ce) or europium (Eu) in a composite metal oxide or a metal sulfide.

Specifically, examples of the phosphor include Y ₃ Al ₅ O ₁₂ :Ce (YAG (Yttrium Aluminum Garnet): Ce), and (Y, Gd) ₃ (Al, Ga). ₅ O ₁₂ :Ce, Tb ₃ Al ₃ O ₁₂ :Ce, Lu ₃ Al ₃ O ₁₂ :Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce, Lu ₂ CaMg ₂ (Si,Ge) ₃ O ₁₂ :Ce, etc. a garnet-type phosphor having a garnet-type crystal structure; for example, (Sr, Ba) ₂ SiO ₄ : Eu, Ca ₃ SiO ₄ Cl ₂ : Eu, Sr ₃ SiO ₅ : Eu, Li ₂ SrSiO ₄ : Eu, Ca ₃ Si ₂ O ₇ : Eu silicate phosphor; for example, aluminate phosphor such as CaAl ₁₂ O ₁₉ :Mn, SrAl ₂ O ₄ :Eu; for example, ZnS: Cu, Al, CaS: Eu, CaGa ₂ S ₄ : sulfide phosphor such as Eu, SrGa ₂ S ₄ :Eu; for example, CaSi ₂ O ₂ N ₂ :Eu, SrSi ₂ O ₂ N ₂ :Eu, BaSi ₂ O ₂ N ₂ :Eu, Ca-α- An oxynitride phosphor such as SiAlON; a nitride phosphor such as CaAlSiN ₃ :Eu or CaSi ₅ N ₈ :Eu; a fluoride-based phosphor such as K ₂ SiF ₆ :Mn or K ₂ TiF ₆ :Mn; . Preferably, a garnet type phosphor is used, and further preferably, Y ₃ Al ₅ O ₁₂ :Ce(YAG) is used.

The phosphors may be used alone or in combination of two or more.

When the phosphor layer is formed into a phosphor ceramic plate, the phosphor layer is used as a ceramic material, and the ceramic material is sintered to obtain a phosphor layer (fluorescent ceramic). Or may The raw material of the above phosphor is sintered, and a phosphor layer (fluorescent ceramic) is obtained by the chemical reaction generated thereby.

Further, when the phosphor ceramic is obtained, an additive such as a binder resin, a dispersant, a plasticizer, or a sintering aid may be added at an appropriate ratio before sintering.

On the other hand, when the phosphor layer is formed of the phosphor resin composition, for example, the phosphor resin composition is prepared by first blending the phosphor and the resin.

The resin is a matrix in which a phosphor is dispersed, and examples thereof include a transparent resin such as a polyoxyxylene resin composition, an epoxy resin, and an acrylic resin. From the viewpoint of durability, a polyoxyxylene resin composition is preferred.

The polyoxyxylene resin composition mainly has a main chain having a siloxane chain (-Si-O-Si-) in a molecule, and an alkyl group (for example, a methyl group) bonded to a ruthenium atom (Si) of the main chain. A side chain of an organic group such as an aryl group (e.g., phenyl or the like) or an alkoxy group (e.g., methoxy group).

Specifically, examples of the polyoxyxylene resin composition include a dehydration condensation-curable polyphthalocyanine resin, an addition reaction-curable polyfluorene oxide resin, a peroxide-curable polyfluorene oxide resin, and a moisture-curing type polymerization. A hardening type polyoxyn resin such as a silicone resin.

The dynamic viscosity of the polyoxyxene resin composition at 25 ° C is, for example, 10 to 30 mm ² /s.

The resin may be used singly or in combination of two or more.

The blending ratio of each component is as follows: the blending ratio of the phosphor is, for example, 1% by mass or more, preferably 5% by mass or more, and, for example, 50% by mass or less, relative to the phosphor resin composition. Preferably, it is 30% by mass or less. In addition, the blending ratio of the phosphor to 100 parts by mass of the resin is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and further, for example, 100 parts by mass or less, preferably 40 parts by mass or less.

In addition, the blending ratio of the resin is, for example, 50% by mass or more, preferably 70% by mass or more, and for example, 99% by mass or less, and preferably 95% by mass or less.

The phosphor resin composition is prepared by blending the phosphor and the resin at the above-mentioned blending ratio Prepared by stirring and mixing. The prepared phosphor resin composition is formed into a sheet shape, specifically, a phosphor resin sheet.

In the case where the resin contains a hardening type polyoxyxylene resin, the phosphor resin sheet is formed in a B-stage or a C-stage. Further, in the case where the phosphor resin sheet is formed in the B-stage, it is also possible to form the C stage by heating thereafter.

The phosphor layer is preferably formed of a phosphor ceramic plate from the viewpoint of heat conduction from heat generated by the LED and the phosphor layer.

When the phosphor layer is formed of a phosphor ceramic plate, the thickness is, for example, 50 μm or more, preferably 100 μm or more, and is, for example, 1000 μm or less, or preferably 500 μm or less. Further, in the case of forming a phosphor resin sheet, the thickness is, for example, 25 μm or more, preferably 50 μm or more, and is also, for example, 1000 μm or less, preferably 200 μm, from the viewpoint of film formability and device appearance. the following.

Examples of the polyoxyxylene adhesive composition include a polyfluorene pressure-sensitive adhesive composition, a polyoxyxene thermoplastic-thermosetting adhesive composition, and the like.

The polyoxygen-sensitive pressure-sensitive adhesive composition is prepared, for example, from a raw material containing a first polyoxyalkylene oxide, a second polyoxyalkylene oxide, and a catalyst.

The main raw material of the first polyoxyalkylene-based polyfluorene pressure-sensitive adhesive composition may, for example, be a reactive polyoxyalkylene such as a polyoxyalkylene group containing a decyl alcohol group.

Examples of the polyoxyalkylene group having a stanol group include polyoxyalkylene having a decyl alcohol group at both ends.

The polyoxyalkylene group having a decyl alcohol group at both ends is an organic siloxane having a stanol group (SiOH group) at both ends of the molecule, and is specifically represented by the following formula (A).

General formula (A):

(In the formula (A), R ^a represents ^a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group; and n represents an integer of 1 or more)

In the above-mentioned general formula (A), among the monovalent hydrocarbon groups represented by R ^a , the saturated hydrocarbon group may, for example, be a linear or branched alkyl group having 1 to 6 carbon atoms (methyl or ethyl group). A propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group or the like), for example, a cycloalkyl group having 3 to 6 carbon atoms (cyclopentyl group, cyclohexyl group or the like).

In the above-mentioned general formula (A), among the monovalent hydrocarbon groups represented by R ^a , examples of the aromatic hydrocarbon group include an aryl group (phenyl group, naphthyl group) having 6 to 10 carbon atoms.

In the above formula (A), R ^a may be the same or different from each other, and is preferably the same.

The monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group or a phenyl group.

In the above formula (A), n is preferably an integer of 10,000 or less, and more preferably an integer of 1,000 or less.

Further, n in the above formula (A) is calculated as an average value.

Specific examples of the polyoxyalkylene group having a decyl alcohol group at both ends include polydimethyl methoxy oxane having a decyl alcohol group at both ends, and polymethyl phenyl siloxane having a decyl alcohol group at both ends. A polydiphenyl fluorene or the like having a decyl alcohol group at both ends.

Such a first polyoxyalkylene oxide may be used singly or in combination of plural kinds.

Among the first polyoxyalkylenes, polydimethyloxane having a decyl alcohol group at both ends is preferably used.

A commercial product may be used as the first polyoxyalkylene, or may be used according to a known method. Adult.

The number average molecular weight of the first polyoxyalkylene is, for example, 100 or more, preferably 200 or more, and is, for example, also 1,000,000 or less, preferably 100,000 or less. The number average molecular weight is calculated by gel permeation chromatography in terms of standard polystyrene.

The blending ratio of the first polyoxyalkylene oxide is, for example, 60% by mass or more, preferably 80% by mass or more, and, for example, 99.5% by mass or less, preferably in the polyoxymethylene pressure-sensitive adhesive composition. 98% by mass or less.

The auxiliary material of the second polyoxyalkylene-based polyoxo pressure-sensitive adhesive composition is added as needed, for example, in order to obtain characteristics such as improvement in hardness of the adhesive layer 4, improvement in adhesion, and improvement in heat resistance. Examples of the second polyoxyalkylene oxide include a chain polyoxyalkylene oxide and a cyclic polyoxyalkylene oxide. Preferable examples are cyclic polyoxoxanes.

The cyclic polyoxyalkylene is represented by the following formula (B).

(In the general formula (B), R ^a has the same meaning as R ^a in the general formula (A). m represents an integer of 2 or more)

m is preferably an integer of 3 or more, and is, for example, an integer of 10 or less, preferably an integer of 6 or less.

Specific examples of the cyclic polysiloxane are hexamethylcyclotrioxane (in the formula (B), R ^a is a methyl group, m is 3), and octamethylcyclotetraoxane (general formula) In (B), R ^a is a methyl group, m is 4), decamethylcyclopentaoxane (in the formula (B), R ^a is a methyl group, m is 5), and the like.

Such a second polyoxyalkylene oxide may be used singly or in combination of plural kinds.

Among the second polyoxyalkylenes, octamethylcyclotetraoxane is preferred.

The blending ratio of the second polyoxyalkylene is, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the first polyoxyalkylene.

Examples of the catalyst include a peroxide, and examples of such a peroxide include benzoic acid benzoate, benzammonium peroxide, methylbenzhydrazide, and benzoic acid toluene. Formyl peroxide is an organic peroxide such as a peroxide.

The catalyst can be used alone or in combination.

As the catalyst, it is preferred to use (mixture) of benzamidine peroxide, benzammonium peroxide, m-methylbenzonitrile, and toluene toluene.

In view of controlling the hardness of the adhesive layer 4, the blending ratio of the catalyst is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, and also 10 parts, per 100 parts by mass of the first polyoxyalkylene oxide. The amount by mass or less is preferably 5 parts by mass or less.

Further, the polyfluorene pressure-sensitive adhesive composition is prepared by disposing the above-mentioned raw materials in a solvent as needed to prepare a varnish, and then, if necessary, reacting them. Examples of the solvent include aromatic hydrocarbons such as toluene.

Further, after the film of the adhesive layer 4 is formed, the above solvent may be distilled off as needed.

Commercially available products can be used as the above-mentioned polyoxygen peroxide pressure-sensitive adhesive composition, and for example, 280A, 282, 7355, 7358, 7502, 7657, Q2-7406, Q2-7566, Q2-7735 manufactured by Dow Corning Co., Ltd. can be used, for example. PIA 590, PSA 600, PSA 595, PSA 610, PSA 518, PSA 6574, PSA 529, PSA 750-D1, PSA 825-D1, PSA 800-C, etc. manufactured by Momentive.

Such a polyoxygen-sensitive pressure-sensitive adhesive composition is prepared, for example, in a liquid or semi-solid shape.

The polyoxyxene thermoplastic-thermosetting adhesive composition has both thermoplasticity and thermosetting properties. Examples of such a polyoxyxene thermoplastic-thermosetting adhesive composition include a first polyfluorinated thermoplastic-thermosetting adhesive composition and a second polyoxy-thermoplastic thermosetting adhesive composition. Third polyoxyl thermoplastic-thermosetting adhesive composition, fourth polyoxyl A thermoplastic-thermosetting adhesive composition, a fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition, and a sixth polyoxy-thermoplastic thermosetting adhesive composition.

The first polyoxyl thermoplastic-thermosetting adhesive composition contains, for example, a two-terminal amine-based polyoxyxylene resin composition, a diisocyanate, and a radical generator.

The both-end amine-based polyoxyxylene resin composition is preferably a compound represented by the following formula (1) from the viewpoint of transparency or high heat resistance.

(wherein A to D are structural units, A and D are terminal units, B and C are repeating units, R ¹ represents a monovalent hydrocarbon group, R ² represents an alkenyl group, R ³ represents an alkylene group, and a represents 0 or more. An integer, b represents an integer of 0 or more. a+b satisfies the relationship of an integer of at least 1 or more. All R ¹ may be the same or different, and b R ² may be the same or different)

The compound represented by the formula (1) is a compound composed of the structural units A, B, C and D, and the terminal unit contains an amine group (-NH ₂ ).

Formula (1), the hydrocarbon group represented by R ^1, for example, of a saturated or aromatic hydrocarbon group. The carbon number of the hydrocarbon group is, for example, from 1 to 20, preferably from 1 to 10, from the viewpoint of availability.

Examples of the saturated hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group or a cyclopentyl group. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a benzyl group or a tolyl group.

The hydrocarbon group represented by R ¹ is preferably a methyl group or a phenyl group from the viewpoint of transparency and light resistance of the first polyfluorene oxide thermoplastic-thermosetting adhesive composition obtained. To list the methyl groups. Further, in the formula (1), all of R ^{1 are} preferably independently a structural unit, and each independently represents the above hydrocarbon group.

The formula R (1) in the ^2, include the substituted or unsubstituted alkenyl group. Specifically, the organic group having an alkenyl group in the skeleton may be a vinyl group, an allyl group, a butynyl group, a pentynyl group or a hexynyl group. Among these, a vinyl group is preferred from the viewpoint of transparency and heat resistance of the first polyfluorene thermoplastic-thermosetting adhesive composition obtained.

As R ³ in the formula (1), for example, a substituted or unsubstituted alkylene group can be mentioned. R ³ is not particularly limited as long as it is an organic group having an alkylene group in the skeleton, and the organic group is used in view of transparency and heat resistance of the first polyfluorene-thermoplastic thermosetting adhesive composition obtained. The carbon number is, for example, 1 to 10. Specific examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Among them, from the viewpoint of transparency and heat resistance of the first polyoxyxene thermoplastic thermosetting adhesive composition obtained, a propyl group is preferred. Further, in the formula (1), all of R ³ , that is, two R ^{3 's} may be the same or different.

The structural unit A is an end unit, specifically, it is contained at one end of the molecule. That is, the formula (1) contains one structural unit A.

The structural unit D is an end unit, specifically, it is contained at the other end of the molecule on the opposite side to the structural unit A. That is, the formula (1) contains one structural unit D.

The number of repeating units of the structural unit B, that is, a in the formula (1) represents an integer of 0 or more, and is, for example, 1 in view of transparency of the first polyfluorene-thermoplastic thermoplastic-thermosetting adhesive composition obtained. ~10,000, preferably an integer from 10 to 10,000.

The b of the structural unit C, that is, the b in the formula (1) is, for example, 0 to 10,000, preferably from 0 to 10,000, from the viewpoint of the transparency of the first polyoxyxene thermoplastic-thermosetting adhesive composition obtained. An integer from 0 to 1,000.

The sum of a and b is preferably from 1 to 10,000, and more preferably from 10 to 10,000. Furthermore, since the sum of a and b is at least an integer of 1 or more, either one of a or b may be 0.

A commercially available product can be used as the two-terminal amine-based polyoxyxylene resin composition represented by the formula (1), or can be synthesized according to a known method.

The weight average molecular weight of the both terminal amine-based polyoxyxyl resin composition represented by the formula (1) is, for example, from 100 to 1,000,000, preferably from 1,000 to 100,000, from the viewpoint of stability or workability. The weight average molecular weight is measured by gel permeation chromatography (GPC (Gel Permeation Chromatography): standard polystyrene equivalent), and the same applies hereinafter.

The content of the both-end amine-based polyoxyxylene resin composition is, for example, 1% by mass or more, preferably 80% by mass or more, in the first polyoxyxene thermoplastic-thermosetting adhesive composition, and is also, for example, 99.9 mass% or less.

The diisocyanate is represented, for example, by the following formula (2) from the viewpoint of compatibility with each component.

Equation (2): O=C=N-Y-N=C=O (2)

(wherein Y represents a divalent hydrocarbon group)

As Y in the formula (2), for example, a saturated or unsaturated linear, branched or cyclic hydrocarbon group can be mentioned. The carbon number of the hydrocarbon group is, for example, from 1 to 50, preferably from 1 to 30, from the viewpoint of availability and heat resistance of the obtained first polyoxyxene thermoplastic-thermosetting adhesive composition.

Examples of the diisocyanate include aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, and the like. Specific examples thereof include hexamethylene diisocyanate, 4,4'-methylene dicyclohexylene diisocyanate, 4,4'-methylene diphenyl diisocyanate, and 1,3-diazetidinyl-2,4- Diketo-bis(4,4'-methylenedicyclohexyl)diisocyanate, 1,3-diazetidinyl-2,4-dione-bis(4,4'-methylenediphenyl)di Isocyanate, tetramethylene benzene dimethylene diisocyanate, isophorone diisocyanate, toluene 2,4-diisocyanate, dicyclohexylmethylene diisocyanate, etc., which may be used alone or Two or more types can be used in combination. Among these, from the viewpoints of transparency, heat resistance, and availability, toluene 2,4-diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate are preferred.

As the diisocyanate, a commercially available product can be used, or it can be synthesized according to a known method.

The content of the diisocyanate is, for example, 1.0 × 10 ^-5 mass% or more, and is, for example, 20 mass% or less, preferably 10 mass% or less, in the first polyoxyl thermoplastic-thermosetting adhesive composition.

Further, in terms of the mass ratio of the amine group of the both terminal amine-based polyoxyxylene resin composition to the isocyanate group of the diisocyanate, the mass ratio of the terminal amino group-type polyoxyxyl resin composition to the diisocyanate The molar ratio (amine/isocyanate group) of the functional groups is, for example, 0.1/1 to 1/0.1, preferably substantially equal (1/1).

The radical generating agent is a compound which generates a radical and promotes crosslinking reaction between the two terminal amino group-type polyoxyxyl resin compositions, and examples thereof include a photoradical generating agent or an organic peroxide, etc., due to the first polyfluorene thermoplastic Since the thermosetting adhesive composition exhibits thermoplasticity/thermosetting property depending on the temperature, an organic peroxide which generates a radical by heating is preferably used.

Specific examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetamidine peroxide, 1,1-di(perylene peroxide)-3,3,5. -trimethylcyclohexane, 1,1-di(dihexyl peroxide)cyclohexane, 1,1-di(t-butylperoxy)-2-methylcyclohexane, 1,1- Di(t-butylperoxide)cyclohexane, 2,2-di(t-butylperoxy)butane, 2,2-bis(4,4-di-(peroxybutyl)cyclohexyl) Propane, hydroperoxide p-menthane, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide , dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, tributyl cumyl peroxide, di-tertiary hexyl peroxide , di-tert-butyl peroxide, diisobutylphosphonium peroxide, di-n-octyl peroxide, diphenyl peroxide Formamidine, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxycarbonate, third hexyl peroxy neodecanoate, new peroxidation Tert-butyl citrate, tert-butyl peroxybutyrate, tert-butyl peroxypropylene monocarbonate, tert-butylbenzene peroxide, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoints of transparency, heat resistance and availability, di-tert-butyl peroxide and 2,5-dimethyl-2,5-di(peroxybutylene peroxide) are preferred. Hexane, tributylbenzene peroxide.

Although it is not possible to determine the temperature at which the radical generating agent generates radicals, it may be, for example, 100 ° C or higher.

A commercially available product can be used as the radical generating agent, and it can also be synthesized according to a known method.

The content of the radical generating agent is, for example, 1.0 × 10 ^-6 % by mass or more, and for example, 20% by mass or less, preferably 10% by mass, based on the first polyfluorene-thermoplastic thermoplastic-thermosetting adhesive composition. the following.

Further, when the amount of the R ¹ group of the both terminal amine-based polyoxyxene resin composition is 100 mol%, the flexibility of the obtained first polyfluorene thermoplastic-thermosetting adhesive composition is maintained. In view of the above, the content of the radical generating agent is, for example, 0.001 mol% or more, preferably 0.01 mol% or more, and further, for example, 50 mol% or less, preferably 10 mol% or less.

The first polyoxyl thermoplastic-thermosetting adhesive composition is not particularly limited as long as it contains a terminal amino group-type polyoxyxylene resin composition, a diisocyanate, and a radical generator.

The first polyfluorene-thermoplastic thermoplastic-thermosetting adhesive is selected from the viewpoints of the reaction mechanism of the reaction between the isocyanate group and the crosslinking reaction using a radical generator, and the reaction temperature and time are appropriately selected to complete and complete the reaction. The composition is preferably a component which is previously associated with the reaction of an isocyanate group, that is, a two-terminal amine-based polyoxyxylene resin composition and diisocyanate. The acid ester is mixed, and then the radical generating agent is formulated.

The compounding of the component related to the reaction of the isocyanate group is carried out by, for example, at 0 ° C or higher, preferably 10 ° C or higher, and further, for example, 100 ° C or lower, preferably 60 ° C or lower. The resin composition, the diisocyanate, and an optional organic solvent are stirred, for example, for 0.1 to 40 hours.

The organic solvent is not particularly limited, and from the viewpoint of improving the compatibility of the respective components, a ketone such as methyl ethyl ketone is preferred.

Further, one part of the reaction between the amine group of the two-terminal amine-based polyoxyxylene resin composition and the isocyanate group of the diisocyanate can be started by the above-mentioned mixing, and the progress of the reaction can be performed by ¹ H-NMR (Nuclear Magnetic Resonance, The nuclear magnetic resonance measurement was confirmed by the degree of disappearance of the peak derived from the amine group.

Next, as a component related to the crosslinking reaction, a radical generating agent is mixed in a mixture of components related to the reaction of the above isocyanate group. When the first polyfluorene-thermoplastic thermoplastic-thermosetting adhesive composition is subjected to two kinds of reactions of a reaction between an isocyanate group and a crosslinking reaction using a radical generator to obtain a cured product, it can be obtained by generating a crosslinking reaction. The cured product (molded product) is not particularly limited as long as the radical generating agent is uniformly mixed in a mixture of the components related to the reaction of the above isocyanate group.

Specifically, a radical generator is prepared and stirred and mixed in a mixture of a two-terminal amine-based polyoxyxyl resin composition and a diisocyanate. The mixing time cannot be determined depending on the reaction temperature or the kind and amount of the components to be reacted, but may be, for example, 0.1 to 40 hours. Further, the obtained mixture (reactant) can be subjected to removal of a solvent or the like according to a known method.

The first polyoxyxene thermoplastic-thermosetting adhesive composition thus obtained is solid at normal temperature, exhibits a thermoplastic behavior at 40° C. or higher, and exhibits thermosetting properties at 50° C. or higher.

Specifically, the thermoplastic temperature of the first polyoxyxene thermoplastic-thermosetting adhesive composition is preferably 40 ° C or higher, more preferably 80 ° C or higher, and still more preferably 200 ° C or lower, and further preferably. It is below 150 ° C ° C. Further, the thermoplastic temperature-based first polyoxyxene thermoplastic-thermosetting adhesive composition exhibits a thermoplastic temperature, specifically, a solid polyoxyx thermoplastic-thermosetting adhesive composition. The temperature which softens by heating and becomes completely liquid, is substantially the same as the softening temperature.

Further, the thermosetting temperature of the first polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is preferably 100 ° C or higher, more preferably 130 ° C or higher, and still more preferably 200 ° C or lower. The thermosetting temperature is a temperature at which the first polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition exhibits thermosetting properties, and specifically, it is a liquid-like first polyfluorinated thermoplastic-thermosetting adhesive composition. It is hardened by heating and completely becomes a solid temperature.

The second polyoxyl thermoplastic-thermosetting adhesive composition contains, for example, a two-terminal amine-based polyoxyxylene resin composition, an organic hydrogen polyoxyalkylene oxide, a diisocyanate, and a hydrazine hydrogenation catalyst.

The two-terminal amine-based polyoxyxene resin composition in the second polyoxyxene thermoplastic-thermosetting adhesive composition is exemplified as the first polyfluorinated thermoplastic-thermosetting adhesive composition. The both terminal amine-based polyoxyxylene resin compositions are the same.

The content of the both-end amine-based polyoxyxylene resin composition is, for example, 1 to 99.5% by mass, preferably 80 to 99.5% by mass, based on the second polyfluorinated thermoplastic-thermosetting adhesive composition.

The organohydrogen polyoxyalkylene is a polyoxyalkylene containing a hydroquinonealkyl group (-SiH). More specifically, the organohydrogenpolyoxyalkylene is a side chain type organohydrogenpolyoxyalkylene having a linear chain and bonded to the main chain and having a hydroquinone group, and/or hydrogen at both ends of the molecule. A two-terminal organohydrogenpolyoxyalkylene group of a decyl group.

The side chain type organic hydrogen polyoxyalkylene is represented, for example, by the following formula (3).

Equation (3):

(wherein E to H represent a structural unit, E and H represent a terminal unit, F and G represent a repeating unit, and R ⁴ represents a monovalent hydrocarbon group. Further, e represents an integer of 0 or more, and f represents an integer of 1 or more)

E~H constitutes a side chain type organic hydrogen polyoxyalkylene.

In the formula (3), the one-valent hydrocarbon group represented by R ⁴ may be the same or different, and is preferably the same.

Examples of the monovalent hydrocarbon group represented by R ⁴ include the same ones as the ones represented by R ^{1 in} the above formulas (1) and (2), and a methyl group and a phenyl group are preferred, and more preferably listed. methyl.

From the viewpoint of reactivity and stability, e preferably represents an integer of from 1 to 10,000, and more preferably represents an integer of from 1 to 5,000.

f is preferably 2 or more, and preferably represents an integer of 1 to 10000 from the viewpoint of reactivity and stability, and more preferably represents an integer of 1 to 1000, and is solid at room temperature. From the viewpoint of imparting flexibility to the polyoxyxene resin composition, it is particularly preferable to represent an integer larger than e, and it is preferably an integer of from 100 to 1,000.

Examples of the side chain type organohydrogenpolyoxane include methylhydroquinoxane, dimethyloxane-co-methylhydroquinone, ethylhydroquinone, and methylhydroquinone. Alkane-co-methylphenyl fluorene and the like.

The number average molecular weight of the side chain type organohydrogenpolysiloxane is, for example, from 200 to 100,000, preferably from 200 to 80,000, from the viewpoint of stability and workability.

The side chain type organic hydrogen polyoxyalkylene can be synthesized, for example, according to a known method, or A commercially available product (for example, manufactured by Gelest Corporation, Shin-Etsu Chemical Co., Ltd.) can be used.

The two-terminal type organic hydrogen polyoxyalkylene is represented, for example, by the following formula (4).

(wherein R to U represent a structural unit, R and U represent a terminal unit, and S and T represent a repeating unit. R ⁵ represents a monovalent hydrocarbon group selected from a saturated hydrocarbon group and an aromatic hydrocarbon group. Further, g represents an integer of 0 or more. , t represents an integer greater than 0)

R~U constitutes a two-terminal organic hydrogen polyoxyalkylene.

In the formula (4), the one-valent hydrocarbon group represented by R ⁵ may be the same or different, and is preferably the same.

As one of the monovalent hydrocarbon group represented by R ⁵ include the same as the above-described formula (1) represented by R ¹ to one of those monovalent hydrocarbon, monovalent hydrocarbon group, preferably a methyl group, a phenyl group, and further preferably List the methyl groups.

From the viewpoint of reactivity and stability, g is preferably an integer of 0 or more, more preferably an integer of 1 to 10,000, and particularly preferably an integer of 1 to 5,000.

From the viewpoint of reactivity and stability, t is preferably an integer of 0 or more, more preferably an integer of 1 to 10,000, and particularly preferably an integer of 1 to 5,000.

For example, when t is 1 or more, the two-terminal organohydrogenpolyoxyalkylene is a side chain of an autonomous chain branch and a side chain containing a hydrogen atom at both ends of the main chain - both ends have an organic polymerization of hydrogen Specific examples of the oxane include a methylhydrogenpolyoxyalkylene having a hydroquinone at both ends and a hydroxanyl group at both ends (dimethylpolyoxane-co-methylhydropolysiloxane). Ethylhydropolysiloxane having a hydroquinone at both ends and hydroquinone at both ends (methyl hydrogen) Polyoxyalkylene-co-methylphenyl polyoxyalkylene) and the like. Further, for example, when t is 0, the two-terminal organohydrogenpolysiloxane is such that the side chain of the autonomous chain branch does not contain a hydrogen atom, and the side chain containing a hydrogen atom at both ends of the main chain does not contain hydrogen/two. The organic polyoxosiloxane containing a hydrogen at the end may specifically be a polydimethyl methoxy alkane having a hydroquinone at both ends, a polymethylphenyl siloxane having a hydroxanyl group at both ends, and a hydroxane at both ends. Polydiphenyl sulfoxane and the like. As the two-terminal organohydrogenpolysiloxane, it is preferred that the side chain represented by the formula (5) contains no hydrogen/organopolyoxyalkylene having hydrogen at both terminals.

(wherein R ⁵ represents a monovalent hydrocarbon group selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group. Further, g represents an integer of 1 or more)

In the formula (5), the one-valent hydrocarbon group represented by R ⁵ may be the same or different, and is preferably the same.

In the formula (5), R ⁵ represents the same meaning as described above, and g represents the same meaning as described above.

The number average molecular weight of the two-terminal organohydrogenpolysiloxane is, for example, from 100 to 30,000, preferably from 100 to 10,000, from the viewpoint of stability and workability.

The two-terminal type organic hydrogen polyoxyalkylene can be synthesized, for example, according to a known method, or a commercially available product can also be used.

The content of the hydroquinone group in the organohydrogen polyoxyalkylene is, for example, specifically 0.01 mmol/g or more, preferably 0.05 mmol/g or more, and further, for example, 20 mmol/g or less, preferably 15 mmol/g. the following. The hydroquinone content was calculated from the integral value of the hydroquinone group and the methyl group by ¹ H-NMR.

The organic hydrogen polyoxyalkylene can be synthesized, for example, according to a known method, or a commercially available product (for example, manufactured by Gelest Corporation, Shin-Etsu Chemical Co., Ltd.) can also be used.

The content of the organic hydrogen polyoxyalkylene oxide is, for example, 0.0001% by mass or more, preferably 0.001% by mass or more, and, for example, 90% by mass or less, in the second polyfluorinated thermoplastic-thermosetting adhesive composition. It is preferably 50% by mass or less.

Further, from the viewpoint of reacting the alkenyl group of the both terminal amine-based polyoxyxylene resin composition with the SiH group (hydroindolyl group) of the organic hydrogen polyoxyalkylene, the two-terminal amine-based polyoxyl The mass ratio of the resin composition to the organohydrogenpolyoxane, and the molar ratio (alkenyl/SiH group) of the functional group is, for example, 1/1 to 0.1/1, preferably 1/1 to 0.2/1, and further Good is 1/1~0.5/1, especially preferably equal (1/1).

The diisocyanate may be the same as the diisocyanate exemplified as the first polyfluorinated thermoplastic-thermosetting adhesive composition.

The content of the diisocyanate is, for example, 1.0 × 10 ^-5 mass% or more, and is, for example, 20 mass% or less, preferably 10 mass% or less, in the second polyoxyl thermoplastic-thermosetting adhesive composition.

Further, in terms of the mass ratio of the amine group of the both terminal amine-based polyoxyxylene resin composition to the isocyanate group of the diisocyanate, the mass ratio of the terminal amino group-type polyoxyxyl resin composition to the diisocyanate The molar ratio of the functional group (amino/isocyanate group) is, for example, 1/1 to 0.1/1, preferably 1/1 to 0.2/1, more preferably 1/1 to 0.5/1, and particularly preferably Essentially equal (1/1).

The ruthenium hydrogenation catalyst is not particularly limited as long as it is a compound which can catalyze the hydrogenation reaction of an alkenyl group of a two-terminal amine-based polyoxyxylene resin composition with a hydrofluorenyl group of an organic hydrogen polyoxyalkylene oxide, and is not particularly limited. For example, a platinum catalyst such as platinum black, platinum chloride, chloroplatinic acid, a platinum-olefin complex, a platinum-carbonyl complex, or a platinum-acetic acid acetate such as a palladium catalyst such as a rhodium catalyst.

The content of the ruthenium hydrogenation catalyst in the second polyoxyxene thermoplastic-thermosetting adhesive composition, for example, in the case of using a platinum catalyst, relative to the organic hydrogen polyoxymethane from the viewpoint of the reaction rate 100 parts by mass, the platinum content is, for example, 1.0 × 10 ^-10 parts by mass or more, preferably 1.0 × 10 ^-8 parts by mass or more, and further, for example, 0.5 parts by mass or less, preferably 1.0 × 10 ^-3 parts by mass or less. .

Further, the second polyoxy-thermoplastic thermosetting adhesive composition contains a component of a two-terminal amine-based polyoxyxylene resin composition, an organic hydrogen polyoxyalkylene oxide, a diisocyanate, and a hydrogenation catalyst. It is prepared without particular limitation.

The second polyoxyxene thermoplastic-thermosetting adhesive composition may be premixed in view of the reaction temperature and time depending on the respective reaction mechanisms of the reaction between the isocyanate group and the hydrogenation reaction, and the reaction proceeds and ends. The components associated with the reaction of the isocyanate groups are remixed with the components associated with the rhodium hydrogenation reaction.

The mixing of the components related to the reaction of the isocyanate group can be carried out by, for example, 0 ° C or higher, preferably 10 ° C or higher, and, for example, 100 ° C or lower, preferably 60 ° C or lower. The resin composition, the diisocyanate, and an optional organic solvent are stirred, for example, for 0.1 to 40 hours.

The organic solvent is not particularly limited, and from the viewpoint of improving the compatibility of the respective components, a ketone such as methyl ethyl ketone is preferred.

Further, a part of the reaction between the amine group of the two-terminal amine-based polyoxyxylene resin composition and the isocyanate group of the diisocyanate may be started by the above mixing, and the progress of the reaction may be determined by ¹ H-NMR, according to the source. The degree of disappearance of the peak of the amine group was confirmed.

Thereafter, as a component related to the hydrogenation reaction of the hydrazine, an organic hydrogen polyoxyalkylene oxide and a hydrazine hydrogenation catalyst are blended in a mixture of components related to the reaction of the above isocyanate group.

Since the second polyoxyl thermoplastic-thermosetting adhesive composition can produce the above-mentioned hydrogenation reaction by using the subsequent heating to obtain a cured product (shaped product), the components related to the hydrogenation reaction of the hydrogen are uniformly mixed. The mixing method is not particularly limited as long as it is a mixture of the components related to the reaction of the above isocyanate groups.

Specifically, an organic hydrogen polyoxyalkylene oxide and a ruthenium hydrogenation catalyst are blended in a mixture of a two-terminal amine-based polyoxyxylene resin composition and a diisocyanate, followed by stirring and mixing. The mixing time cannot be determined depending on the reaction temperature or the kind and amount of the components to be reacted, but may be, for example, 0.1 to 40 hours. The mixing method is not particularly limited as long as the components are uniformly mixed. Further, the obtained mixture can be subjected to removal of a solvent or the like according to a known method.

The second polyoxyxene thermoplastic-thermosetting adhesive composition thus obtained is solid at normal temperature, exhibits a thermoplastic behavior at 40° C. or higher, and exhibits thermosetting properties at 50° C. or higher.

Specifically, the thermoplastic temperature of the second polyoxyxene thermoplastic-thermosetting adhesive composition is, for example, 40 to 200 ° C, preferably 40 to 150 ° C.

Further, at the next thermal curing temperature, the second polyfluorene-thermoplastic thermosetting adhesive composition is subjected to a hydrazine hydrogenation reaction to thermally cure the second polyfluorene oxide thermoplastic-thermosetting adhesive composition.

The heat curing temperature is, for example, 100 to 200 ° C, preferably 130 to 200 ° C. Further, the progress of the hydrogenation reaction of hydrazine can be confirmed by ¹ H-NMR, and the signal intensity derived from the amine group derived from the amine-based polyoxyxylene resin composition at both ends is confirmed, and the reaction is regarded as the end of the reaction at the stage where the signal disappears.

The third polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition can be obtained by reacting a cage sesquioxaxane with an alkenyl group-containing polyoxyalkylene in the presence of a rhodium hydrogenation catalyst.

The octamer of a cage-type sesqui-sesquioxanes-based trifunctional polyoxyl monomer, specifically, has 8 groups represented by the following formula (6), and the formula (6):

(wherein R ⁶ represents a monovalent hydrocarbon group, and R ⁷ represents a hydrogen or a monovalent hydrocarbon group. Among them, the average value of the R ⁷ one-valent hydrocarbon group: hydrogen molar ratio is based on the average of the cage-type sesquioxane as a whole. 6.5: within the range of 1.5~5.5:2.5)

More specifically, it is represented by the following formula (7).

(wherein R ⁶ and R ^{7 have} the same meanings as defined above. Further, the molar ratio of the one-valent hydrocarbon group of R ⁷ : hydrogen is the same as above)

In the above formulae (6) and (7), the monovalent hydrocarbon group represented by R ⁶ is, for example, a saturated hydrocarbon group or an aromatic hydrocarbon group.

Examples of the saturated hydrocarbon group include a linear saturated hydrocarbon group (for example, methyl group, ethyl group B). a base having a carbon number of 1 to 6 such as a propyl group, a butyl group, a pentyl group or a hexyl group, or a branched saturated hydrocarbon group (for example, an alkyl group having 3 to 6 carbon atoms such as an isopropyl group or an isobutyl group) or a cyclic group A saturated hydrocarbon group (for example, a cycloalkyl group having 3 to 6 carbon atoms such as a cyclohexyl group).

Examples of the aromatic hydrocarbon group include an aryl group having 6 to 8 carbon atoms such as a phenyl group, a benzyl group and a tolyl group.

The carbon number of the monovalent hydrocarbon group is, for example, 1 to 8, preferably 1 to 6.

R ⁶ may be identical or different, preferably the same.

The monovalent hydrocarbon group is preferably a saturated linear hydrocarbon group from the viewpoint of easiness of preparation and thermal stability, and more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. .

In the above formulae (6) and (7), the one-valent hydrocarbon group represented by R ⁷ may be the same as the one-valent hydrocarbon group represented by the above R ¹ . Preferably, a methyl group is exemplified.

The one-valent hydrocarbon group of R ⁷ in the formula (7): the molar ratio of hydrogen is in the range of 6.5:1.5 to 5.5:2.5, preferably 6.0, based on the average value of the cage-type sesquioxane. Within the range of 2.0~5.5:2.5.

That is, 1.5 to 2.5 (specifically 2) groups represented by the above formula (6) are formed in one molecule of the cage octapestane, and preferably 2 to 2.5 (specifically 2) are formed. Hydroquinone (-SiH).

In the case where the above-mentioned R ⁷ one-valent hydrocarbon group: hydrogen molar ratio exceeds 6.5/1.5 (= 6.5: 1.5) (for example, 7/1 (=7:1)), the number of moles of hydroquinone is too small, so The degree of reaction of the cage-type sesquioxaxane with the alkenyl group-containing polyoxyalkylene is excessively lowered, and the molecular weight of the obtained third polyoxyxa thermoplastic-thermosetting adhesive composition is lowered, and a solid state cannot be obtained. The case of a polyoxyl thermoplastic-thermosetting adhesive composition.

On the other hand, to one of the divalent hydrocarbon group having ⁷ R: hydrogen molar ratio of less than 5.5 / 2.5 (= 5.5: 2.5) of the case (e.g., 5/3 (= 5: 3)), the cage octasilsesquioxane The hydrohaloalkyl group of the decane has an excessive number of moles, and therefore, the third polyfluorene thermoplastic-heat is caused by an excessive increase in the degree of reaction of the cage sesquioxane to the alkenyl group-containing polyoxyalkylene. The hardenable adhesive composition does not exhibit thermoplasticity.

Specific examples of the above-mentioned cage-type sesquioxaxane include, in the above formulae (6) and (7), R ⁶ is a methyl group, R ⁷ is a methyl group or hydrogen, and the cage type is eight and a half times. The average of the total amount of the decane, the methyl group of R ⁷ : a cage type octapestane having a molar ratio of hydrogen of 5.5:2.5, 6:2 or 6.5:1.5.

The cage type sesquisestasiloxane represented by the above formula (7) can be synthesized, for example, according to a known method (for example, according to JP-A-2007-246880).

Specifically, a tetraalkoxy decane (such as tetraethoxy decane) is reacted in the presence of an alcohol such as methanol and/or water and a catalyst to synthesize an octa (sesquioxane) skeleton (formula (7) a portion other than the group of the formula (6), and thereafter, a dialkyl chlorodecane (dimethyl chlorodecane, etc.) is blended at a ratio corresponding to the above-mentioned R ⁷ one-valent hydrocarbon group: hydrogen molar ratio. And a trialkyl chlorodecane (trimethylchloromethane, etc.), an alkoxy group (ethoxy group, etc.) bonded to a ruthenium atom of an octa sesquioxane skeleton, and a dialkyl chlorodecane and a triane The chloropurane is reacted. After the reaction, the reactants were purified as needed. Thereby, cage type sesquioxaxane can be obtained.

Further, a commercially available product can also be used as the cage type sesquioxane.

The alkenyl group-containing polyoxyalkylene is a polyoxyalkylene group having an alkenyl group at both ends of the molecule and having an alkenyl group, and is specifically represented by the following formula (8).

(wherein R ⁸ represents a monovalent hydrocarbon group, and R ⁹ represents an alkenyl group. Further, i represents an integer of 1 or more)

In the formula (8), the one-valent hydrocarbon group represented by R ⁸ may be the same or different, and is preferably the same.

Examples of the monovalent hydrocarbon group represented by R ⁸ include the same ones as the ones represented by R ^{6 in} the above formulae (6) and (7), and a methyl group or a phenyl group is preferred, and more preferably methyl.

In the formula (8), examples of the alkenyl group represented by R ⁹ include a substituted or unsubstituted alkenyl group, and preferably an unsubstituted alkenyl group.

Examples of such an alkenyl group include an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a propenyl group, a butenyl group or a pentenyl group.

The number of carbon atoms of the alkenyl group is, for example, 2 to 10, preferably 2 to 5.

R ⁹ may be the same or different, preferably the same.

The alkenyl group is preferably an alkyl group having 2 to 5 carbon atoms, and more preferably a vinyl group, from the viewpoint of reactivity with the hydroalkylene group of the cage sesquioxaxane.

From the viewpoint of reactivity and stability, i preferably represents an integer of from 1 to 5,000, and more preferably represents an integer of from 1 to 1,000.

The number average molecular weight of the alkenyl group-containing polyoxyalkylene represented by the above formula (8) is, for example, 100 or more, preferably 300 or more, and, for example, 10,000 or less, from the viewpoint of safety and handling. It is preferably 5,000 or less.

The alkenyl group-containing polyoxyalkylene represented by the above formula (8) can be synthesized, for example, according to a known method, or a commercially available product (for example, manufactured by Gelest Co., Ltd.) can also be used.

The rhodium hydrogenation catalyst is the same as the rhodium hydrogenation catalyst exemplified in the second polyfluorinated thermoplastic thermosetting adhesive composition, and from the viewpoint of compatibility and transparency, platinum is preferably used. Further, the catalyst is preferably a platinum-olefin complex, and specific examples thereof include platinum such as platinum-1,3-divinyl-1,1,3,3-tetramethyldioxane complex. Divinyl oxime complex and the like.

Further, a ruthenium hydrogenation catalyst can also be prepared as a known solvent (toluene or the like) solution.

The blending ratio of the rhodium hydrogenation catalyst (solid content) is 100 parts by mass based on the total amount of the cage sesquioxane and the alkenyl group-containing polyoxane, and is, for example, 1.0 × 10 ^-10 parts by mass or more. It is preferably 1.0 × 10 ^-8 parts by mass or more, and is, for example, 3 parts by mass or less, preferably 1 part by mass or less.

Further, in the presence of a rhodium hydrogenation catalyst, the molar number of the hydrofluorenyl group of the cage-type sesquioxaxane becomes more (excess) than the number of moles of the alkenyl group of the alkenyl group-containing polyoxyalkylene. The method comprises reacting a cage of sesquioxaxane with an alkenyl group-containing polyoxyalkylene.

The molar ratio of the alkenyl group to the hydrofluorenyl group (the molar number of the alkenyl group/the molar number of the hydrofluorenyl group) is less than 1, and is, for example, 0.10 to 0.99, preferably 0.20 to 0.99, and more preferably 0.50 to 0.99. .

On the other hand, when the above molar ratio exceeds the above range, the hydrofluorenyl group becomes less than the alkenyl group, and in this case, there is no excess hydroquinone group remaining after the reaction and no third polyfluorene oxide is present. The thermoplastic-thermosetting adhesive composition imparts thermosetting properties.

Further, in order to react the above-mentioned cage sesquioxane with a polyoxyalkylene group containing an alkenyl group, the above-mentioned compounding ratio is used together with the hydrazine hydrogenation catalyst and the solvent, and then it is necessary to Wait for heating.

The solvent may, for example, be an aromatic hydrocarbon such as toluene, or an aliphatic hydrocarbon such as hexane, or an ester such as ethyl acetate. From the viewpoint of improving the compatibility of the respective components, an aromatic hydrocarbon is preferred, and toluene is more preferred.

The reaction temperature is, for example, 0 ° C or higher, preferably 20 ° C or higher, and further, for example, 100 ° C or lower, preferably 80 ° C or lower, and the reaction time is, for example, 0.5 to 96 hours.

Thereby, the hydroquinone alkyl group of the cage sesquioxanes and the alkenyl group of the alkenyl group-containing polyoxyalkylene are subjected to a hydrazine hydrogenation reaction.

Further, the degree of the hydrogenation reaction of hydrazine can be confirmed by ¹ H-NMR, and the signal intensity derived from the alkenyl group derived from the alkenyl group-containing polyoxyalkylene can be confirmed, and when the signal disappears, it is regarded as the end of the hydrogenation reaction.

In the above hydrogenation reaction, the caged sesquioxanes are reacted with the alkenyl group-containing polyoxane in such a manner that the mole number of the hydroquinone group is excessive compared with the mole number of the alkenyl group. After the reaction, an excess of hydroquinone is left, and the excess hydroquinone is bonded to each other by hydrolysis and condensation reaction with water in the air by heating (for example, heating at 100 to 200 ° C) ( By three-dimensional cross-linking, the third polyfluorene-thermoplastic thermoplastic-thermosetting adhesive composition is given thermosetting property.

Thereby, a third polyoxyl thermoplastic-thermosetting adhesive composition can be obtained.

The obtained third polyoxyxene thermoplastic-thermosetting adhesive composition was a solid. The occlusion resistance of the alkenyl group-containing polyoxyalkylene is lowered by the steric hindrance of the cage sesquioxane, and therefore, the third polyoxyl thermoplastic-thermosetting adhesive composition is obtained as a solid.

The thermoplastic temperature of the third polyoxyl thermoplastic-thermosetting adhesive composition is, for example, 40 ° C or higher, preferably 50 ° C or higher, and is also, for example, 100 ° C or lower, preferably 90 ° C or lower.

The thermosetting property of the temporarily plasticized third polyoxyl thermoplastic-thermosetting adhesive composition is bonded to each other by hydrolysis and condensation reaction of excess hydroquinone by heating by subsequent heating (three-dimensional intersection) Union) to performance.

Further, the thermosetting temperature of the third polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is, for example, 150 ° C or higher, preferably 180 ° C or higher, and is, for example, 300 ° C or lower, preferably 250 ° C or lower.

The fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition contains a cage-type sesquioxane alkane, an alkenyl group-containing polyoxane, a hydrazine hydrogenation catalyst, and a hydroxyl group-containing polyoxyalkylene.

The cage type sesquioxaxane, the alkenyl group-containing polyoxane and the hydrazine hydrogenation catalyst in the fourth polyoxy-thermoplastic thermosetting adhesive composition may be exemplified by the third polyoxyl thermoplastic- The alkenyl-containing polyoxyalkylene exemplified in the cage-type sesquioxaxane and the third polyfluorene thermoplastic-thermosetting adhesive composition exemplified in the thermosetting adhesive composition, and The ruthenium hydrogenation catalyst exemplified in the second polyoxyl thermoplastic-thermosetting adhesive composition is the same.

The polyoxyalkylene group having a hydroxyl group is, for example, a polyoxyalkylene group containing a plurality of (for example, two) hydroxyl groups, and more specifically, a terminal polysiloxane having a hydroxyl group at both terminals of the molecule. Specifically, the polyoxyalkylene containing a hydroxyl group is represented by the following formula (9).

(wherein R ¹⁰ represents a monovalent hydrocarbon group. Further, j represents an integer of 1 or more)

In the formula (9), the one-valent hydrocarbon group represented by R ¹⁰ may be the same or different, and is preferably the same.

Examples of the monovalent hydrocarbon group represented by R ¹⁰ include the same ones as the ones represented by R ^{6 in} the above formulae (5) and (6), and a methyl group and a phenyl group are preferred, and more preferably listed. methyl.

From the viewpoint of reactivity and stability, j preferably represents an integer of from 1 to 10,000, and more preferably represents an integer of from 1 to 5,000.

The number average molecular weight of the hydroxyl group-containing polyoxosiloxane represented by the above formula (9) is, for example, 100 or more, preferably 500 or more, and, for example, also 100,000 or less, from the viewpoint of safety and handling. Good for 50,000 or less.

The polyoxyalkylene group having a hydroxyl group represented by the above formula (9) can be synthesized, for example, according to a known method, or a commercially available product (for example, manufactured by Gelest Co., Ltd.) can also be used.

Further, the fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is obtained by using a cage of sesquioxaxane, an alkenyl group-containing polyoxane, a ruthenium hydrogenation catalyst, and a hydroxyl group-containing polyoxyl The alkane is prepared by blending.

The blending ratio of the cage-type sesquioxaxane is, for example, 1% by mass or more, preferably 5% by mass or more, and, for example, 50%, based on the fourth polyoxy-thermo-thermosetting thermosetting adhesive composition. The mass% or less is preferably 40% by mass or less.

The ratio of the alkenyl group-containing polyoxane is such that the number of moles of the alkenyl group of the alkenyl group-containing polyoxyalkylene becomes less than the number of moles of the hydroquinone of the cage sesquioxanes. Make adjustments.

That is, the molar ratio of the alkenyl group to the hydrofluorenyl group (the molar number of the alkenyl group/the molar number of the hydroalkylene group) is less than 1, and is, for example, 0.10 to 0.99, preferably 0.20 to 0.99, and more preferably 0.50. ~0.99.

When the above molar ratio exceeds the above range, the hydrofluorenyl group becomes less than the alkenyl group. In this case, there is no excess hydroquinone alkyl group remaining after the reaction, and the fourth polyfluorene oxide thermoplastic-thermosetting layer is not present. The case where the adhesive composition imparts thermosetting properties.

On the other hand, when the molar ratio is less than the above range, the hydroquinone group remains excessively, and the cage sesquioxanes are hardened by hydrolysis and self-condensation due to moisture in the air. Get the softness situation.

The blending ratio of the rhodium hydrogenation catalyst (solid content) is 100 parts by mass based on the total amount of the cage sesquioxane and the alkenyl group-containing polyoxane, and is, for example, 1.0 × 10 ^-10 parts by mass or more. It is preferably 1.0 × 10 ^-8 parts by mass or more, and is, for example, 3 parts by mass or less, preferably 1 part by mass or less.

The compounding ratio of the hydroxyl group-containing polyoxyalkylene is obtained by subtracting the alkenyl group-containing polyoxane from the molar number of the hydroxyl group (X) relative to the molar number of the hydrofluorenyl group of the cage-type sesquioxaxane. The molar number (Y) of the molar number of the alkenyl group of the alkane is, for example, 0.001 or more, preferably 0.01 or more, in terms of the molar ratio (X/Y), and is, for example, 1000 or less, preferably 100. Adjust in the following ways. In other words, the compounding ratio of the hydroxyl group-containing polyoxyalkylene is 100 parts by mass relative to the total amount of the cage sesquioxanes and the alkenyl group-containing polyoxyalkylene, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and further, for example, 50 parts by mass or less, preferably 30 parts by mass or less.

When preparing the fourth polyfluorene thermoplastic-thermosetting adhesive composition, it is preferred to react the cage sesquioxanes with the alkenyl group-containing polyoxane in the presence of a rhodium hydrogenation catalyst. The obtained polyoxyxylene resin composition precursor was formulated with a hydroxyl group-containing polyoxane.

That is, first, in the presence of a rhodium hydrogenation catalyst, the molar number of the hydrofluorenyl group of the cage-type sesquiterpene oxide becomes more than the number of moles of the alkenyl group of the alkenyl group-containing polyoxane. In a manner, a cage type sesquioxane is reacted with an alkenyl group-containing polyoxyalkylene to obtain a polyoxyxylene resin composition precursor.

In order to obtain a polyoxyxylene resin composition precursor, more specifically, the above-mentioned cage type sesquioxaxane and an alkenyl group-containing polyoxane, a hydrogenation catalyst, and an optional solvent are used in the above ratio. The preparation is carried out together, after which the heating is carried out as needed.

The solvent may, for example, be an aromatic hydrocarbon such as toluene, or an aliphatic hydrocarbon such as hexane, or an ester such as ethyl acetate. From the viewpoint of improving the compatibility of the respective components, an aromatic hydrocarbon is preferred, and toluene is more preferred.

The reaction temperature is, for example, 0 ° C or higher, preferably 20 ° C or higher, and further, for example, 100 ° C or lower, preferably 80 ° C or lower, and the reaction time is, for example, 0.5 to 96 hours.

Thereby, the cage sesquioxanes are reacted with an alkenyl group-containing polyoxyalkylene. That is, the hydroquinone alkyl group of the cage sesquioxanes and the alkenyl group of the polyoxyalkylene group having an alkenyl group are subjected to a hydrazine hydrogenation reaction.

Further, the degree of hydrogenation of the hydroquinone alkyl group of the cage sesquioxanes with the alkenyl group of the alkenyl group-containing polyoxyalkylene can be determined by ¹ H-NMR, based on the aggregation derived from the alkenyl group. The signal intensity of the alkenyl group of the decane is confirmed, and when the signal disappears, it is regarded as the end of the hydrogenation reaction.

In the above hydrogenation reaction, the molar number of the hydroquinone alkyl group and the molar number of the alkenyl group The caged sesquioxaxane is reacted with an alkenyl group-containing polyoxyalkylene in such a manner as to be excessive, and an excess of hydroquinone is left after the reaction.

Thereby, a polyoxyxylene resin composition precursor was obtained.

Further, the precursor of the polyoxymethylene resin composition is liquid or semi-solid.

Then, the obtained polyoxyxylene resin composition precursor and the hydroxyl group-containing polyoxyalkylene are blended at the above ratio. The polyoxyxylene resin composition precursor is reacted with a hydroxyl group-containing polyoxyalkylene by heating thereafter. Further, the solvent is distilled off as needed.

Thereby, a fourth polyoxyl thermoplastic-thermosetting adhesive composition can be obtained.

The obtained fourth polyoxyxene thermoplastic-thermosetting adhesive composition was a solid. The occlusion resistance of the alkenyl group-containing polyoxyalkylene is lowered by the steric hindrance of the cage sesquioxaxane, so that the fourth polyfluorene thermoplastic-thermosetting adhesive composition is obtained as a solid.

The thermoplasticity of the fourth polyoxyl thermoplastic-thermosetting adhesive composition is expressed by the improvement of the mobility of the cage sesquioxane and the alkenyl group-containing polyoxyalkylene by heating.

The thermoplastic temperature of the fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is, for example, 40 ° C or higher, preferably 50 ° C or higher, and is, for example, 150 ° C or lower, preferably 100 ° C or lower.

The thermosetting property of the temporarily plasticized fourth polyoxyl thermoplastic-thermosetting adhesive composition is specifically retained by the precursor of the fourth polyoxyl thermoplastic-thermosetting adhesive composition. The hydroquinone is represented by a reaction with a hydroxyl group of a hydroxyl group-containing polyoxyalkylene.

More specifically, the hydroquinone alkyl group of the cage type sesquioxanes in the precursor of the fourth polyoxy-thermo-thermosetting adhesive composition is subjected to a condensation reaction with a hydroxyl group of a polyoxyalkylene group containing a hydroxyl group.

Further, the fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition has a relatively low heat curing temperature, and is, for example, 100 ° C or higher, preferably 120 ° C or higher, and, for example, 250 ° C or lower. The thermosetting temperature is a 4th polyoxyl thermoplastic-thermosetting adhesive composition showing heat The temperature of the hardenability, specifically, the temperature at which the plasticized fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is hardened by heating and completely becomes a solid.

Since the fourth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition contains a polyoxyalkylene containing a hydroxyl group, the hydroxyl group of the polyoxyalkylene group having a hydroxyl group and the residual hydroalkylalkyl group of the cage-type sesquioxaxane The reaction is carried out whereby cross-linking sesquioxaxane can be crosslinked. Therefore, the flexibility of the fourth polyoxyethylene thermoplastic-thermosetting adhesive composition can be improved.

Further, the heat hardening temperature (for example, 100 to 250 ° C) of the fourth polyoxyethylene thermoplastic-thermosetting adhesive composition can be lowered.

The fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition contains a cage-type sesquioxaxane, an alkenyl group-containing polyoxane, a hydrazine hydrogenation catalyst, and an organic hydrogen polyoxyalkylene.

In the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition, the cage sesquioxanes, the alkenyl-containing polyoxyalkylene and the hydrazine hydrogenation catalyst may be respectively exemplified with the fourth polyoxyl thermoplastic- The cage type sesquioxaxane, the alkenyl group-containing polyoxane, and the hydrazine hydrogenation catalyst exemplified in the thermosetting adhesive composition are the same. The hydroquinone content in the fifth polyoxyl thermoplastic-thermosetting adhesive composition is, for example, 0.01 mmol/g or more, preferably 0.05 mmol/g or more, and further preferably 20 mmol/g or less, preferably. It is 15 mmol/g or less.

In the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition, the organohydrogenpolyoxyalkylene may be exemplified as the organic hydrogen polyoxyalkylene exemplified in the second polyoxyxene thermoplastic-thermosetting adhesive composition. The same.

Further, the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is obtained by using cage-type sesquioxaxane, alkenyl group-containing polyoxyalkylene oxide, hydrazine hydrogenation catalyst, and organic hydrogen polyoxyalkylene oxide. Prepared by blending.

The blending ratio of the cage sesquioxaxane is, for example, 10 to 80% by mass, preferably 10 to 70% by mass, based on the fifth polyfluorene thermoplastic-thermosetting adhesive composition.

The ratio of the alkenyl group-containing polyoxane is such that the number of moles of the alkenyl group of the alkenyl group-containing polyoxyalkylene becomes less than the number of moles of the hydroquinone of the cage sesquioxanes. Enter Line adjustment.

That is, the molar ratio of the alkenyl group to the hydrofluorenyl group (the molar number of the alkenyl group/the molar number of the hydrofluorenyl group) is less than 1, and is, for example, 0.10 to 0.99, preferably 0.20 to 0.99, more preferably 0.50~0.99.

When the above molar ratio exceeds the above range, the hydrofluorenyl group becomes less than the alkenyl group. In this case, the excess hydroquinone group is not sufficiently retained after the reaction, and the fifth polyfluorene oxide thermoplastic-heat is not present. The case where the curable adhesive composition imparts thermosetting property.

On the other hand, when the molar ratio is less than the above range, the hydroquinone group remains excessively, and the cage sesquioxanes are hardened by hydrolysis and self-condensation due to moisture in the air. Get the softness situation.

The blending ratio of the rhodium hydrogenation catalyst (solid content) is 100 parts by mass based on the total amount of the cage sesquioxane and the alkenyl group-containing polyoxane, and is, for example, 1.0 × 10 ^-10 parts by mass or more. It is preferably 1.0 × 10 ^-8 parts by mass or more, and is also, for example, 3 parts by mass or less, preferably 1 part by mass or less.

The compounding ratio of the organohydrogen polyoxyalkylene is obtained by subtracting the alkenyl group-containing polyfluorene from the molar number (X) of the hydroquinone group relative to the molar number of the hydroquinone group of the cage-type sesquioxaxane. The molar number (Y) of the number of moles of the alkenyl group of the oxyalkylene is, for example, 0.001 or more, preferably 0.01 or more, in terms of the molar ratio (X/Y), and is, for example, 1,000 or less, preferably Adjust by 100 or less. In other words, the compounding ratio of the organohydrogenpolysiloxane is 100 parts by mass, for example, 0.01 to 100 parts by mass, preferably 0.01, based on 100 parts by mass of the total of the cage type sesquioxane and the alkenyl group-containing polysiloxane. ~50 parts by mass.

Further, the compounding ratio of the organohydrogenpolyoxyalkylene to the fifth polyfluorene-oxygen thermoplastic-thermosetting adhesive composition is, for example, 0.01 to 50% by mass, preferably 0.01 to 30% by mass.

When preparing the fifth polyfluorene thermoplastic-thermosetting adhesive composition, it is preferred to reverse the cage sesquioxanes with the alkenyl group-containing polyoxane in the presence of a rhodium hydrogenation catalyst. The obtained polyoxymethylene resin composition precursor is formulated with an organic hydrogen polyoxyalkylene oxide.

That is, first, in the presence of a rhodium hydrogenation catalyst, the molar number of the hydrofluorenyl group of the cage-type sesquiterpene oxide becomes more than the number of moles of the alkenyl group of the alkenyl group-containing polyoxane. The blending ratio allows the cage sesquioxane to react with the alkenyl group-containing polyoxyalkylene, thereby obtaining a polyoxyxylene resin composition precursor.

In order to obtain a polyoxyxylene resin composition precursor, more specifically, the above-mentioned cage type sesquioxaxane and an alkenyl group-containing polyoxane, a hydrogenation catalyst, and an optional solvent are used in the above ratio. The preparation is carried out together, after which the heating is carried out as needed.

The solvent may, for example, be an aromatic hydrocarbon such as toluene, or an aliphatic hydrocarbon such as hexane, or an ester such as ethyl acetate. From the viewpoint of improving the compatibility of the respective components, an aromatic hydrocarbon is preferred, and toluene is more preferred.

The reaction temperature is, for example, 0 ° C or higher, preferably 20 ° C or higher, and further, for example, 100 ° C or lower, preferably 80 ° C or lower, and the reaction time is, for example, 0.5 to 96 hours.

Thereby, the cage sesquioxanes are reacted with an alkenyl group-containing polyoxyalkylene. That is, the hydroquinone alkyl group of the cage sesquioxanes and the alkenyl group of the polyoxyalkylene group having an alkenyl group are subjected to a hydrazine hydrogenation reaction.

Further, the degree of hydrogenation of the hydroquinone alkyl group of the cage sesquioxanes with the alkenyl group of the alkenyl group-containing polyoxyalkylene can be determined by ¹ H-NMR, based on the aggregation derived from the alkenyl group. The signal intensity of the alkenyl group of the decane is confirmed, and when the signal disappears, it is regarded as the end of the hydrogenation reaction.

In the above hydrogenation reaction, the caged sesquioxaxane is reacted with an alkenyl group-containing polyoxyalkylene in such a manner that the mole number of the hydroquinone alkyl group is excessive compared with the molar number of the alkenyl group. Excess hydroquinone will remain after this reaction.

Thereby, a polyoxyxylene resin composition precursor was obtained.

Further, the precursor of the polyoxymethylene resin composition is liquid or semi-solid.

Then, the precursor of the polyoxyxene resin composition obtained by the above ratio is blended with Machine hydrogen polyoxane. The polyoxyxylene resin composition precursor is reacted with an organic hydrogen polyoxyalkylene by heating thereafter (described below). Further, the solvent is distilled off as needed.

Thereby, the fifth polyoxyl thermoplastic-thermosetting adhesive composition can be obtained.

The obtained fifth polyoxyxene thermoplastic-thermosetting adhesive composition was a solid. The occlusion resistance of the alkenyl group-containing polyoxyalkylene is lowered by the steric hindrance of the cage sesquioxane, so that the fifth polyoxyl thermoplastic-thermosetting adhesive composition is obtained as a solid.

Further, since the molar ratio of the one-valent hydrocarbon group:hydrogen of R ⁷ of the fifth polyfluorene thermoplastic-thermosetting adhesive composition is within a specific range, in the cage type sesquioxane, the pair contains The ratio of the hydroxanyl group in which the alkenyl group of the alkenyl polyoxyalkylene is reacted is adjusted. Further, the alkenyl group-containing polyoxyalkylene is formed in such a manner that the molar number of the alkenyl group becomes smaller than the molar number of the hydroquinone of the cage sesquioxanes and the cage sesquioxaxane Carry out the reaction. Therefore, the obtained fifth polyoxyxene thermoplastic-thermosetting adhesive composition is excellent in transparency and heat resistance, and can have both thermoplasticity and thermosetting property.

That is, the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is temporarily plasticized (or liquidized) by the above heating, and then thermally cured.

The thermoplasticity of the fifth polyoxyl thermoplastic-thermosetting adhesive composition is expressed by the motility of the cage-type sesquioxane and the alkenyl group-containing polyoxyalkylene by heating.

Further, the thermoplastic temperature of the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is, for example, 40 ° C or higher, preferably 50 ° C or higher, and further preferably 150 ° C or lower, preferably 100 ° C or lower. Further, the thermoplastic temperature-based fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition exhibits a thermoplastic temperature, specifically, a solid fifth-polyoxy-thermoplastic-thermosetting adhesive composition. The temperature which softens by heating and becomes completely liquid, and is substantially the same as the softening temperature.

The thermosetting property of the temporarily plasticized fifth polyoxyxene thermoplastic-thermosetting adhesive composition, specifically, the hydroquinone remaining in the precursor of the polyoxyalkylene resin composition It is represented by a reaction with a hydroalkylene group of an organic hydrogen polyoxyalkylene.

More specifically, the hydroquinone alkyl group of the cage sesquioxaxane and the hydroquinone alkyl group of the organic hydrogen polyoxyalkylene in the precursor of the polyoxyxylene resin composition are reacted (hydrolyzed) with water in the air to carry out Dehydration (intermolecular dehydration) condensation reaction.

Further, the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition has a relatively low heat curing temperature, and is, for example, 100 ° C or higher, preferably 120 ° C or higher, and, for example, 250 ° C or lower. The thermosetting temperature is a temperature at which the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition exhibits thermosetting properties, specifically, a plasticized fifth polyfluorene-oxygen thermoplastic-thermosetting adhesive composition. The temperature which hardens by heating and becomes completely solid.

In the fifth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition, the hydroalkylene group of the organohydrogenpolyoxyalkylene is reacted with the residual hydroalkylene group of the cage sesquioxanes. That is, the cage type sesquioxane can be crosslinked by a dehydration (intermolecular dehydration) condensation reaction. Therefore, the flexibility of the fifth polyfluorene thermoplastic-thermosetting adhesive composition can be improved.

Further, the heat hardening temperature (for example, 100 to 250 ° C) of the fifth polyfluorene thermoplastic-thermosetting adhesive composition can be lowered.

The sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition contains a caged sesquioxaxane, a polyoxyalkylene having an alkenyl group at both terminals, a hydrazine hydrogenation catalyst, and a polyoxyl group having an alkenyl group in a side chain. alkyl.

In the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition, the cage sesquioxaxane, the polyoxyalkylene group having an alkenyl group at both terminals, and the rhodium hydrogenation catalyst are exemplified by the third polyfluorene oxide thermoplastic. - a cage-type sesquioxaxane exemplified in the thermosetting adhesive composition, and a polyoxyalkylene group having an alkenyl group at both terminals exemplified in the third polyfluorinated thermoplastic-thermosetting adhesive composition, The ruthenium hydrogenation catalyst exemplified in the second polyoxyl thermoplastic-thermosetting adhesive composition is the same.

The side chain contains a polyoxyalkylene having 2 alkenyl groups on the side chain of the polyoxyalkylene group having an alkenyl group. Examples of the polyoxyalkylene group having an alkenyl group in such a side chain include bonding to a linear chain. a side chain of a main chain (the ruthenium atom) of the oxirane moiety (-Si-O-) having an alkenyl group containing a linear azide, and/or containing and branching A branched azepine-containing polyoxyalkylene having an alkene-bonded alkenyl group in the form of a heptane.

The polyoxyalkylene containing a linear alkane is specifically represented by the following formula (10).

(wherein, I to L are structural units, I and L are terminal units, and J and K are repeating units. R ¹¹ represents a monovalent hydrocarbon group, and R ¹² represents an alkenyl group. Further, k represents an integer of 0 or more, and m represents 2 The above integer)

I~L constitutes a polyoxyalkylene containing a linear alkane.

In the formula (10), the one-valent hydrocarbon group represented by R ¹¹ may be the same or different, and is preferably the same.

The monovalent hydrocarbon group represented by R ¹¹ may be the same as the one of the valent hydrocarbon groups represented by R ¹ in the above formula (1), and a methyl group or a phenyl group is preferred, and a methyl group is more preferred.

From the viewpoint of reactivity and stability, k is preferably an integer of from 1 to 10,000, and more preferably an integer of from 1 to 5,000.

From the viewpoint of reactivity and stability, m preferably represents an integer of 2 to 500, and more preferably represents an integer of 2 to 100.

The number average molecular weight of the polyoxane containing a linear alkane is, for example, from 200 to 1,000,000, preferably from 200 to 80,000, from the viewpoint of stability and workability.

The vinyl content of the polyoxyalkylene containing a linear alkane is, for example, 0.01 mmol/g or more, preferably 0.1 mmol/g or more, and is, for example, 10 mmol/g or less, preferably 5 mmol/g or less. The vinyl content of the polyoxyalkylene containing a linear alkane was measured by ¹ H-NMR from the area ratio of the vinyl group to the methyl group.

The polyoxyalkylene containing a linear alkane can be synthesized, for example, according to a known method, or a commercially available product (for example, manufactured by Gelest Co., Ltd.) can also be used.

The polyoxyalkylene containing a branched alkane is specifically represented by the following formula (11).

(Wherein, M, N, P, and Q structural units, M, N and P represent repeating units, Q represents a terminal unit .R ¹³ represents a monovalent hydrocarbon group and, n represents an integer of 1, p and q represents 0 The above integer, r represents an integer of 4 or more. Further, at least two R ¹³ per molecule are alkenyl groups)

M, N, P and Q constitute a polyoxyalkylene containing a branched alkane.

The monovalent hydrocarbon group represented by R ¹³ is, for example, a saturated hydrocarbon group, an aromatic hydrocarbon group, or an unsaturated hydrocarbon group (excluding an aromatic hydrocarbon group).

Examples of the saturated hydrocarbon group and the aromatic hydrocarbon group include the same ones as the ones represented by R ¹ in the above formula (1), and a methyl group and a phenyl group are preferred, and a methyl group is more preferred.

The unsaturated hydrocarbon group (excluding the aromatic hydrocarbon group) is the same as the alkenyl group represented by R ² in the above formula (1), and preferably a vinyl group.

In the formula (11), the monovalent hydrocarbon group represented by R ¹³ contains at least an alkenyl group, preferably an alkyl group and/or a phenyl group and an alkenyl group, and more preferably a methyl group and a vinyl group.

The number of alkenyl groups in the polyoxyalkylene containing a branched alkane is 2 or more, preferably 3 or more, and usually 30 or less.

n preferably represents an integer from 1 to 100, and more preferably represents an integer from 1 to 50.

p preferably represents an integer from 1 to 100, and more preferably represents an integer from 1 to 50.

q preferably represents an integer from 1 to 100, and more preferably represents an integer from 1 to 50.

r preferably represents an integer from 4 to 100, and more preferably represents an integer from 4 to 30.

The number average molecular weight of the polyoxyalkylene containing a branched aluminoxane is, for example, 100 or more, preferably 200 or more, and is also, for example, 10,000 or less, preferably 8,000, from the viewpoint of stability and workability. the following.

The vinyl content of the polyoxyalkylene containing a branched alkane is, for example, 0.01 mmol/g or more, preferably 0.1 mmol/g or more, and is also, for example, 100 mmol/g or less, and is also 10 mmol/g or less. The vinyl content of the polyoxyalkylene containing a branched alkane was measured by ¹ H-NMR from the area ratio of the vinyl group to the methyl group.

The polyoxyalkylene containing a branched alkane can be synthesized, for example, according to a known method, or a commercially available product (for example, manufactured by Gelest Corporation) can also be used.

Further, the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is obtained by using a cage-type sesquioxaxane, a polyoxyalkylene having an alkenyl group at both terminals, a hydrogenation catalyst, and a side chain containing an alkene. The polyoxyalkylene is prepared by compounding.

The blending ratio of the cage octapoxane is, for example, 10 to 80% by mass, preferably 10 to 70% by mass based on the sixth polyoxyl thermoplastic-thermosetting adhesive composition.

The ratio of the polyoxyalkylene containing alkenyl groups at both ends is such that the number of moles of the alkenyl group having a polyoxyalkylene group having an alkenyl group at both ends becomes more than that of the hydroquinone alkyl group of the cage sesquioxane. Adjust in a few ways.

That is, the molar ratio of the alkenyl group to the hydrofluorenyl group (the molar number of the alkenyl group/the molar number of the hydrofluorenyl group) is less than 1, and is, for example, 0.10 to 0.99, preferably 0.20 to 0.99, more preferably 0.50~0.99. In other words, the blending ratio of the polyoxyalkylene group having an alkenyl group at both ends is 100 parts by mass or more, for example, 0.001 part by mass or more based on the total amount of the cage sesquioxane and the polyoxyalkylene having alkenyl groups at both terminals. It is preferably 0.01 parts by mass or more, for example, 30 parts by mass or less, preferably 20 parts by mass or less. Also, it can be used with respect to cage type octadequioxanes and two 100 parts by mass of the total amount of the polyoxyalkylene group having an alkenyl group at the end, and the blending ratio of the polyoxyalkylene group having an alkenyl group at both terminals is, for example, 0.01 parts by mass or more, preferably 0.1 part by mass or more, and further, For example, it is set to 100 parts by mass or less, and preferably set to 50 parts by mass or less.

When the above molar ratio exceeds the above range, the hydrofluorenyl group becomes less than the alkenyl group. In this case, the excess hydroquinone group is not sufficiently retained after the reaction, and the sixth polyfluorene oxide thermoplastic-heat is not present. The case where the curable adhesive composition imparts thermosetting property.

On the other hand, when the molar ratio is less than the above range, the hydroquinone group remains excessively, and the cage sesquioxanes are hardened by hydrolysis and self-condensation due to moisture in the air. Get the softness situation.

The blending ratio of the rhodium hydrogenation catalyst (solid content) is 100 parts by mass based on the total amount of the cage sesquioxane and the polyoxyalkylene having alkenyl groups at both ends, and is, for example, 1.0 × 10 ^-10 parts by mass or more. It is preferably 1.0 × 10 ^-8 parts by mass or more, and is also, for example, 3 parts by mass or less, preferably 1 part by mass or less.

The ratio of the alkenyl group-containing polyoxyalkylene in the side chain is calculated by subtracting the two end groups from the molar number of the alkenyl group (X) relative to the molar number of the hydroquinone group of the cage-type sesquioxaxane. The molar number (Y) of the number of moles of the alkenyl group of the alkenyl polyoxyalkylene is, for example, 0.001 or more, preferably 0.01 in terms of the molar ratio (X/Y), and is, for example, 1000 or less. It is preferable to adjust to 100 or less.

When preparing the sixth polyoxyl thermoplastic-thermosetting adhesive composition, it is preferred to use a octadecyl sulfoxide and an alkenyl group containing an alkenyl group at both ends by the presence of a ruthenium hydrogenation catalyst. The precursor of the sixth polyfluorene thermoplastic-thermosetting adhesive composition obtained by the reaction is blended with a polyoxyalkylene group having an alkenyl group in a side chain.

That is, first, in the presence of a ruthenium hydrogenation catalyst, the number of moles of the hydroquinone group of the cage-type sesquioxaxane becomes larger than the number of moles of the alkenyl group of the polyoxyalkylene group having an alkenyl group at both terminals. (Over) the ratio of the mixture, the cage octapedance and the alkenyl group at both ends The oxane is reacted, whereby a sixth polyfluorene thermoplastic-thermosetting adhesive composition precursor is obtained.

In order to obtain a precursor of the sixth polyoxyl thermoplastic-thermosetting adhesive composition, more specifically, the above-mentioned cage-type sesquioxane and the polyoxyalkylene having alkenyl groups at both ends, The hydrogenation catalyst and the solvent as needed are blended together, and then heated as needed.

The solvent may, for example, be an aromatic hydrocarbon such as toluene, or an aliphatic hydrocarbon such as hexane, or an ester such as ethyl acetate. From the viewpoint of improving the compatibility of the respective components, an aromatic hydrocarbon is preferred, and toluene is more preferred.

The reaction temperature is, for example, 0 ° C or higher, preferably 20 ° C or higher, and further, for example, 100 ° C or lower, preferably 80 ° C or lower, and the reaction time is, for example, 0.5 to 96 hours.

Thereby, the cage sesquioxane is reacted with a polyoxyalkylene having alkenyl groups at both terminals. That is, the hydroquinone group of the cage sesquioxanes and the alkenyl group of the polyoxyalkylene having alkenyl groups at both terminals are subjected to a hydrazine hydrogenation reaction.

Further, the degree of hydrogenation of the hydroquinone group of the cage sesquioxanes with the alkenyl group of the polyoxyalkylene having alkenyl groups at both terminals can be determined by ¹ H-NMR, and the alkenyl group is contained at both ends. The signal intensity of the alkenyl group of the polyoxyalkylene is confirmed, and when the signal disappears, it is regarded as the end of the hydrogenation reaction.

In the above hydrogenation reaction, the caged sesquioxane is reacted with the polyoxyalkylene having alkenyl groups at both ends in such a manner that the mole number of the hydroquinone alkyl group is excessive compared with the molar number of the alkenyl group. Excess hydroquinone will remain after the reaction.

Thereby, a precursor of the sixth polyoxyl thermoplastic-thermosetting adhesive composition was obtained.

Further, the precursor of the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is liquid or semi-solid.

Then, the precursor of the sixth polyfluorene thermoplastic-thermosetting adhesive composition obtained by the above ratio and the polyoxyalkylene group having an alkenyl group in the side chain were prepared at the above ratio. By subsequent heating (below The precursor of the sixth polyfluorene thermoplastic-thermosetting adhesive composition is reacted with a polyoxyalkylene group having an alkenyl group in a side chain. Further, the solvent is distilled off as needed.

Thereby, a sixth polyoxyl thermoplastic-thermosetting adhesive composition can be obtained.

The obtained sixth polyoxyxene thermoplastic-thermosetting adhesive composition was a solid. The sixth polyfluorene thermoplastic-thermosetting adhesive composition is obtained in the form of a solid due to the steric hindrance of the alkenyl group-containing polyoxane at the two ends due to the steric hindrance of the cage sesquioxane. .

Further, since the molar hydrocarbon group of one of the cage-type sesquioxanes of the sixth polyoxy-thermo-thermosetting adhesive composition is in a specific range, it is in the cage type of sesquiterpene. In the oxane, the ratio of the hydroquinone group which reacts with the alkenyl group of the polyoxyalkylene group having an alkenyl group at both terminals is adjusted. Further, the polyoxyalkylene group having an alkenyl group at both ends is such that the molar number of the alkenyl group is less than the molar number of the hydroquinone alkyl group of the cage type sesquioxane and the cage type octadequivalent oxygen The alkane is reacted. Therefore, the obtained sixth polyoxyxene thermoplastic-thermosetting adhesive composition is excellent in transparency and heat resistance and can have both thermoplasticity and thermosetting property.

That is, the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is temporarily plasticized (or liquidized) by the above heating, and then thermally cured.

The thermoplasticity of the sixth polyoxyl thermoplastic-thermosetting adhesive composition is expressed by the improvement of the mobility of the cage sesquioxane and the polyoxyalkylene having alkenyl groups at both ends by heating.

Further, the thermoplastic temperature of the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is, for example, 40 ° C or higher, preferably 50 ° C or higher, and further preferably 150 ° C or lower, preferably 100 ° C or lower. Further, the thermoplastic temperature-based sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition exhibits a thermoplastic temperature, specifically, a solid 6-polyoxy-thermoplastic-thermosetting adhesive composition. The temperature which softens by heating and becomes completely liquid, and is substantially the same as the softening temperature.

The thermosetting property of the temporarily plasticized sixth polyoxyxene thermoplastic-thermosetting adhesive composition is specifically retained by the precursor of the sixth polyfluorene thermoplastic-thermosetting adhesive composition. The hydroquinone group is represented by a reaction with an alkenyl group of a polyoxyalkylene group having an alkenyl group in a side chain.

More specifically, the hydrofluorenyl group of the cage-type sesquioxaxane in the precursor of the sixth polyfluorene thermoplastic-thermosetting adhesive composition and the alkenyl group-containing polyoxyalkylene alkoxy group in the side chain A hydrazine hydrogenation reaction is carried out.

Further, the thermosetting temperature of the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition is relatively low, and is, for example, 100 to 250 ° C, preferably 120 to 250 ° C. The thermosetting temperature is a temperature at which the sixth polyoxy-thermoplastic thermoplastic-thermosetting adhesive composition exhibits thermosetting properties, specifically, a plasticized sixth polyoxyxene thermoplastic-thermosetting adhesive composition. The temperature which hardens by heating and becomes completely solid.

In the sixth polyoxyl thermoplastic-thermosetting adhesive composition, the alkenyl group of the polyoxyalkylene group having an alkenyl group in the side chain and the residual hydroalkylalkyl group of the cage sesquioxaxane are carried out. The reaction can be used to crosslink the cage sesquioxaxane. Therefore, the flexibility of the sixth polyoxyxene thermoplastic-thermosetting adhesive composition can be improved.

Further, the heat hardening temperature (for example, 100 to 250 ° C) of the sixth polyoxyn thermoplastic/thermosetting adhesive composition can be lowered.

The polyoxyxene thermoplastic-thermosetting adhesive composition is formed, for example, in the form of a sheet, a block, or a granular (powder) polymer (see the imaginary line shown in FIG. 2 below). Symbol 9). It is preferably formed into a block-shaped polyoxynitride molded body.

Further, in the phosphor layer adhesive set, the polyether oxide adhesive composition has a percentage of the following peel strength of 30% or more, preferably 35% or more, more preferably 40% or more, and, for example, It is 200% or less, preferably 150% or less.

Percentage of peel strength = [(peel strength PS _{75 ° C in 75 °} C environment) / (peel strength PS _{25 ° C in} 25 ° C environment)] × 100

Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of adhesive formed by a poly-xylene adhesive composition and laminated on a support, adhered to the phosphor layer, and then at a temperature of 75 ° C at a peel angle The peel strength at the time when the support and the adhesive layer were peeled off from the phosphor layer at 180 degrees and at a speed of 300 mm/min. That is, it is the peel strength of the adhesive layer to the phosphor layer in an environment of 75 ° C. Further, the thickness of the adhesive layer in the evaluation of the peel strength was 40 μm.

Peel strength at 25 ° C environment PS _{25 ° C} is a layer of adhesive formed by a poly-xylene adhesive composition and laminated on a support, adhered to the phosphor layer, and then at a temperature of 75 ° C at a peel angle The peel strength at the time when the support and the adhesive layer were peeled off from the phosphor layer at 180 degrees and at a speed of 300 mm/min. That is, it is the peel strength of the adhesive layer to the phosphor layer at 25 ° C. Further, the thickness of the adhesive layer in the evaluation of the peel strength was 40 μm.

If the percentage of the peel strength is less than 30%, there is a problem that the adhesive layer formed of the polyxylene adhesive composition is peeled off from the interface of the phosphor layer.

On the other hand, when the adhesive force of the polyoxymethylene adhesive composition is not more than the above upper limit, the LED 2 (see FIGS. 1 to 9 ) or the LED package 10 (see FIGS. 8 and 9 ) which is the target of adhesion is provided. In this case, the fluorescent adhesive sheet 6 (see Fig. 2(b)) can be temporarily peeled off from the above, and the repair for the maintenance can be easily performed.

Next, the LED-phosphor layer adhesive 1 obtained by using one embodiment of the above-described phosphor layer adhesive set of the present invention will be described with reference to Fig. 1 .

In Fig. 1, an LED-phosphor layer adhesive 1 according to an embodiment of the present invention includes an LED 2, a phosphor layer 3 disposed opposite to the upper side of the LED 2, and a cluster between the LED 2 and the phosphor layer 3. The epoxy adhesive layer 4 is.

The LED 2 has a substantially rectangular plate shape having a substantially rectangular cross section and is formed of a known semiconductor material. Further, although not shown, the LED 2 is provided with an LED-side terminal electrically connected to the substrate-side terminal of the substrate 5 (see FIG. 4) described below.

Further, the polyadox adhesive layer 4 is adhered to the LED 2 and the phosphor layer 3. Further, the adhesive includes a pressure-sensitive adhesive (adhesive) based on the adhesive layer of the polyoxynoxy adhesive layer 4 containing the polyoxygen-containing pressure-sensitive adhesive composition, and a thermoplastic-thermosetting property based on the inclusion of polyfluorene oxide. The polyoxycarbide adhesive layer 4 of the subsequent composition is subjected to thermal hardening followed by thermal hardening followed by adhesion.

From the viewpoint of adhesion (adhesiveness), the thickness of the polyoxygen adhesive layer 4 is, for example, 5 μm or more, and, for example, 200 μm or less, the viewpoint of the heat emitted by the LED 2 and the phosphor layer 3 is transmitted. It is preferably 100 μm or less, more preferably 50 μm or less.

<The first use method of the phosphor layer adhesive set>

Next, as a first method of using the phosphor layer adhesive set, the method of manufacturing the LED-phosphor layer adhesive body 1 is described. Referring to the solid line of FIG. 2, the polyfluorene oxide in the LED-phosphor layer adhesive body 1 is adhered. The following description will be made on the aspect in which the agent layer 4 contains a polyfluorene pressure-sensitive adhesive composition.

In this method, as shown in Fig. 2(a), the phosphor layer 3 is first prepared.

Then, in this method, as shown in Fig. 2(b), the surface layer on the surface of the phosphor layer 3 comprises a polyoxyoxygen adhesive layer 4 of a polyfluorene pressure-sensitive adhesive composition.

Specifically, when the polyfluorene pressure-sensitive adhesive composition is prepared as a varnish, the varnish is applied or dropped on the entire upper surface of the phosphor layer 3. Thereby, the film 4' of the polyfluorene pressure-sensitive adhesive composition is formed. Then, the solvent is distilled off as needed.

Thereby, a polyoxygen oxide adhesive layer 4 (that is, a polyfluorene pressure-sensitive adhesive layer) containing a polyfluorene pressure-sensitive adhesive composition is formed on the surface of the phosphor layer 3.

Thereby, the fluorescent adhesive sheet 6 in which the polyoxygen adhesive layer 4 is laminated on the phosphor layer 3 is obtained.

Thereafter, in this method, as shown in FIG. 2(c), the fluorescent adhesive sheet 6 is bonded to the LED 2. Specifically, the LED 2 and the phosphor layer 3 are pressed by the polyoxygen adhesive layer 4 . That is, the lower surface of the LED 2 is brought into contact with the upper surface of the polyadox adhesive layer 4.

The bonding of the fluorescent adhesive sheet 6 and the LED 2 is performed at a normal temperature (specifically, 20 to 25 ° C). Shi. Alternatively, the fluorescent adhesive sheet 6 may be heated to, for example, 30 to 50 ° C.

Further, the phosphor layer 3 may be pressed against the phosphor layer 3 with an appropriate pressure as needed. Further, depending on the case, the thickness of the polyoxygen adhesive layer 4 can be controlled by the pressing.

Thereby, the LED-phosphor layer adhesive 1 in which the LED 2 and the phosphor layer 3 are pressure-sensitive (adhered) by the polyoxygen adhesive layer 4 is manufactured.

Next, a method of manufacturing the LED device 7 by mounting the LED 2 of the LED-phosphor layer adhesive 1 of Fig. 2(c) on the substrate 5 will be described with reference to Fig. 4 .

In this method, first, as shown in FIG. 4(a), the substrate 5 and the LED-phosphor layer adhesive 1 are prepared separately.

The substrate 5 is formed in a flat shape slightly larger than the LED-phosphor layer adherend 1 in plan view. The substrate 5 includes, for example, an insulating substrate such as a tantalum substrate, a ceramic substrate, a polyimide substrate, or a laminated substrate in which an insulating layer is laminated on a metal substrate.

Further, a conductor pattern (not shown) including a substrate-side terminal (not shown) electrically connected to an LED-side terminal (not shown) of the LED 2 and a wiring connected thereto is formed on the upper surface of the substrate 5. . The conductor pattern is formed, for example, of a conductor such as gold, copper, silver, or nickel.

Further, the LED-phosphor layer adhesive 1 is placed on the upper side of the substrate 5 with the LEDs 2 facing downward.

Then, as shown in FIG. 4(b), the LED 2 of the LED-phosphor layer adhesive body 1 is mounted on the substrate 5. Specifically, an LED-side terminal (not shown) of the LED 2 is flip-chip mounted or wire bonded to a substrate-side terminal (not shown) of the substrate 5. Further, when the LEDs 2 are bonded to the substrate 5 by bonding wires, the fluorescent adhesive sheets 6 adhered to the LEDs 2 are formed to avoid the shape of the bonding wires.

Thereby, the LED device 7 including the substrate 5 and the LED-phosphor layer adhesive 1 and the LED 2 of the LED-phosphor layer adhesive 1 attached to the substrate 5 is obtained.

Further, thereafter, the first sealing layer 8 may be provided on the LED device 7 as shown by the imaginary line in FIG. 4(b) as needed. The first sealing layer 8 is attached to the substrate 5 to cover the LED 2 and the fluorescent paste. The form of the sheet 6 is formed of a transparent resin. After the first sealing layer 8 is placed on the LED device 7, it is adjusted in size, for example, by cutting or the like.

Further, in the phosphor layer adhesive set, the polyether oxide adhesive composition for adhering the phosphor layer 3 to the LED 2 has a peel strength of 30% or more, and is excellent in heat resistance and durability.

In detail, since the adhesion of the polyoxyxylene adhesive composition at a high temperature (for example, a high temperature including 75 ° C) and the adhesion of the polyoxygen adhesive composition to a normal temperature (25 ° C) can be prevented. Compared with the significant reduction, excellent heat resistance can be ensured.

Therefore, the LED device 7 including the LED 2 and the fluorescent adhesive sheet 6 can ensure excellent light-emitting reliability for a long period of time. The fluorescent adhesive sheet 6 is made of a phosphor layer adhesive set manufacturer, and the phosphor layer 3 is included. The polyoxynoxy adhesive layer 4 of the polyoxygen adhesive composition is adhered to the LED 2.

<Second use method of phosphor layer adhesive set>

Next, as a second method of using the phosphor layer adhesive set, the method of manufacturing the LED-phosphor layer adhesive 1 is carried out. Referring to the imaginary line of FIG. 2, the polyoxygen in the LED-phosphor layer adhesive is adhered. The agent layer 4 is described by including a polyoxyxene thermoplastic-thermosetting adhesive composition.

In this method, as shown in FIG. 2(a), the phosphor layer 3 is first prepared.

Thereafter, the phosphor layer 3 is heated. Specifically, the phosphor layer 3 is brought into contact with the hot plate 15 (imaginary line). Specifically, the phosphor layer 3 is placed on the upper surface of the hot plate 15 (hypothetical line).

The temperature of the hot plate 5 is adjusted, for example, to the thermoplastic temperature of the polyfluorene thermoplastic-thermosetting adhesive composition, and specifically, for example, 40 ° C or higher, preferably 50 ° C or higher, more preferably 80 ° C or higher. For example, it is 200 ° C or less, preferably 150 ° C or less, more preferably 100 ° C or less.

Then, in the method, as shown in FIG. 2(b), the surface layer is above the phosphor layer 3. Polyoxygen adhesive layer 4.

Specifically, a polyoxynitride molded body 9 (imaginary line) of the above shape, preferably a block-shaped polyoxynitride molded body 9, is placed on the upper surface of the phosphor layer 3.

For example, the bottom area S1 of the polyoxynitride molded body 9 is smaller than the area S2 of the upper surface of the phosphor layer 3 (S1 < S2), and specifically, the ratio (= S1/S2) is, for example, 0.1 or more, preferably. It is 0.6 or more, and, for example, it is less than 1, preferably 0.95 or less.

When the bottom area S1 of the polyoxynitride molded body 9 is smaller than the area S2 of the upper surface of the phosphor layer 3 (S1 < S2), for example, the polyoxynitride molded body 9 is placed on the upper surface of the phosphor layer 3. Central part.

Further, since the phosphor layer 3 is placed on the hot plate 15 (hypothetical line), heating is performed to plasticize the polyoxynitride molded body 9.

By the above plasticization, the polyoxynitride molded body 9 flows on the upper surface of the phosphor layer 3. For example, when the polyoxynitride molded body 9 is placed on the central portion of the upper surface of the phosphor layer 3, as shown by the imaginary line arrow in Fig. 2(a), the phosphor layer 3 is in the plane direction (along the phosphor layer). The outer side of the direction of the upper surface of the upper surface 3 is specifically diffused from the central portion of the phosphor layer 3 toward the peripheral end portion.

Further, the polyoxynitride molded body 9 flows, for example, without splashing from the upper surface of the phosphor layer 3.

Thereby, as shown in FIG. 2(b), the diffused polyoxyl thermoplastic-thermosetting adhesive composition is laminated on the upper surface of the phosphor layer 3 in a uniform thickness in the plane direction. Thereby, the film 4' of the polyoxyxene thermoplastic-thermosetting adhesive composition is formed on the entire upper surface of the phosphor layer 3.

Then, the LED 2 is laminated on the phosphor layer 3 via the film 4' of the polyoxyxene thermoplastic-thermosetting adhesive composition. That is, the LED 2 is brought into contact with the film 4'.

Thereafter, the phosphor layer 3 in which the LED 2 is laminated via the film 4' is taken out (taken off) from the hot plate 15 (imaginary line), and the phosphor layer 3 is placed on the table at room temperature (20 to 25 ° C). (not shown) the upper surface.

Thereby, the film 4' of the polyfluorene thermoplastic-thermosetting adhesive composition is cooled and solidified.

Thereby, as shown in FIG. 2(b), the polyoxyxylene adhesive layer 4 comprising a solid polyoxyxene thermoplastic-thermosetting adhesive composition (ie, a polyoxyl thermoplastic-thermosetting adhesive layer) The phosphor layer 3 and the LED 2 are next. That is, the polyoxygen adhesive layer 4 is in close contact with the entire upper surface of the phosphor layer 3 and the entire lower surface of the LED 2.

Thereby, the LED-phosphor layer adherend 1 in which the LED 2 and the phosphor layer 3 are followed by the thermal curing by the polyoxygen adhesive layer 4 is produced.

Then, the LED device 7 is manufactured using the LED-phosphor layer adhesive 1.

In the second method of use, the method of manufacturing the LED device 7 using the LED-phosphor layer adhesive 1 is the same as the first method of use shown in FIGS. 4(a) and 4(b).

Further, according to the second method of use, the same effects as those of the first method of use can be exhibited, and further, the polymerized polyoxyxide thermoplastic-thermosetting adhesive composition can be used to form the polyoxygen adhesive layer 4, and therefore, Improves the operability of the phosphor layer adhesive set.

<Other Embodiments>

In the drawings of FIG. 3 and FIG. 5 to FIG. 9 , the same reference numerals are given to the members and the components corresponding to the above-described respective portions, and the detailed description thereof will be omitted.

In the first and second methods of use, as a method of using the phosphor layer adhesive package, as shown in FIG. 2(b), a polysilicon adhesive layer 4 is laminated on the phosphor layer 3 to form a fluorescent layer. After the adhesive sheet 6 is adhered, as shown in Fig. 2(c), the polyoxygen adhesive layer 4 is bonded to the LED 2. On the other hand, for example, as shown in FIG. 3(b), first, a polysilicon adhesive layer 4 is laminated on the LED 2, and thereafter, as shown in FIG. 3(c), a polyoxygen adhesive layer is laminated. 4 is bonded to the phosphor layer 3.

In this method, as shown in FIG. 3(a), the LED 2 is first prepared.

Then, in this method, as shown in FIG. 3(b), the surface of the LED 2 is laminated on the surface of the epoxy adhesive layer 4.

Thereafter, as shown in FIG. 3(c), the polyoxygen adhesive layer 4 is bonded to the phosphor layer 3. Specifically, the lower surface of the phosphor layer 3 is brought into contact with the upper surface of the polyadox adhesive layer 4.

Further, in the embodiment of FIGS. 2 and 3, a polysilicon adhesive layer 4 is laminated on either of the LED 2 and the phosphor layer 3, and thereafter, the polyoxygen adhesive layer 4 is bonded to the other. For example, as shown in FIG. 2(b) and FIG. 3(b), a layer is laminated on both the LED 2 and the phosphor layer 3, and then pasted through two layers of the polyoxygen adhesive layer 4. LED2 and phosphor layer 3 are combined.

In the LED-phosphor layer adhesive 1 of the embodiment of FIG. 1, only the upper surface of the LED 2 is followed by a phosphor layer via the polyoxygen adhesive layer 4, but may be, for example, the upper side of FIG. 5(a). As shown in the figure, the upper surface and the side surface of the LED 2 are adhered via the polysilicon adhesive layer 4.

As shown in the upper side view of Fig. 5(a), a polyoxygen adhesive layer 4 is continuously laminated on the upper surface and the side surface of the LED 2.

Further, a phosphor layer 3 is laminated on the surface (upper surface and side surface) of the polyoxygen adhesive layer 4.

The phosphor layer 3 and the polyfluorinated pressure-sensitive adhesive layer 4 are formed to have a cross section that is opened downward. Word shape.

Thereby, the phosphor layer 3 is adhered to both surfaces of the upper surface and the side surface of the LED 2 via the polyoxygen adhesive layer 4.

In order to obtain the LED-phosphor layer adhesive 1 shown in FIG. 5(a), referring to FIG. 2(a), the phosphor layer 3 is formed in a larger size than the LED 2, and then, referring to FIG. 2(b), in the fluorescent light The entire upper surface area of the bulk layer 3 is layered on the epoxy adhesive layer 4 to obtain a fluorescent adhesive sheet 6 having a size larger than that of the LED 2.

Then, as shown in FIG. 5(a), the fluorescent adhesive sheet 6 is bonded to the LED 2 so that the upper surface of the LED 2 and the side area layer are bonded to the epoxy adhesive layer 4.

Thereby, the LED-phosphor layer adhesive body 1 is obtained.

Thereafter, as shown in FIG. 5(b), the LED device 7 is obtained by mounting the LED 2 of the obtained LED-phosphor layer adhesive 1 on the substrate 5.

Thereafter, as shown by the imaginary line in FIG. 5(b), the first sealing layer 8 is provided on the LED device 7 as needed.

Further, the LED-phosphor layer adherend 1 shown in FIG. 5(a) and the LED device 7 shown in FIG. 5(b) exhibit the same operational effects as described above.

Moreover, in the embodiment of FIG. 4, first, as shown in FIG. 4(a), the LED-phosphor layer adhesive 1 and the substrate 5 are separately formed, and then, as shown in FIG. 4(b), the substrate 5 is formed. The LED2 of the LED-phosphor layer adhesive body 1 is mounted thereon. However, as shown in FIG. 6, the LED 2 may be mounted on the substrate 5 in advance, and the fluorescent adhesive sheet 6 may be separately prepared, and then the LED-phosphor layer adhesive 1 may be formed on the substrate 5.

In the embodiment of Fig. 6, as shown in Fig. 6(b), the LED-phosphor layer adhesive 1 is formed on the substrate 5.

When the LED-phosphor layer adhesive 1 is produced on the substrate 5, first, as shown in FIG. 6(a), the LED 2 previously mounted on the substrate 5 is prepared, and the fluorescent adhesive sheet 6 is separately prepared in advance.

Thereafter, as shown in FIG. 6(b), the phosphor layer 3 is adhered to the LED 2 via the polyoxygen adhesive layer 4.

Thereby, the LED device 7 is obtained.

Further, as shown by the imaginary line in FIG. 6(b), the first sealing layer 8 is provided on the LED device 7 as needed.

According to the embodiment of Fig. 6, the same operational effects as those of the embodiment of Fig. 4 can be exhibited.

Further, as shown in FIG. 7(b), a fluorescent adhesive sheet 6 having a larger size than the LED 2 may be adhered to the upper surface and the side surface of the LED 2 on the substrate 5, and an LED-phosphor layer adhesive layer may be formed on the substrate 5. 1.

In the embodiment of FIG. 7, as shown in FIG. 7(a), the fluorescent adhesive sheet 6 is prepared, and The LED 2 is mounted on the substrate 5 in advance, and thereafter, as shown in Fig. 7(b), the fluorescent adhesive sheet 6 is attached to the upper surface and the side surface of the LED 2.

Thereafter, as shown by the imaginary line in Fig. 7(b), the first sealing layer 8 is provided as needed.

According to the embodiment of Fig. 7, the same operational effects as those of the embodiment of Fig. 6 can be exhibited.

Further, in the embodiment of FIGS. 4 to 7, the fluorescent adhesive sheet 6 is adhered to the LED 2, but it may be adhered to the LED package 10 as shown, for example, in FIG.

In FIG. 8(a), the LED package 10 includes a substrate 5, an LED 2 mounted on the substrate 5, a reflector 11 formed on the substrate 5 and surrounding the LED 2 when projected in the thickness direction, and The second sealing layer 12 of the LED 2 is sealed in the reflector 11.

The LED 2 is mounted on the substrate 5 in advance.

The reflector 11 is formed in a substantially rectangular frame shape or a substantially annular shape (a circular ring shape or an elliptical ring shape) having a central opening in a plan view. Further, the reflector 11 is formed into a substantially trapezoidal shape in which the width is gradually narrowed in the cross section. The reflector 11 is disposed at a distance from the LED 2 so as to surround the LED 2 . That is, the LED 2 is disposed in the reflector 11.

The reflector 11 is formed, for example, of a sintered body of a ceramic material containing a light-reflecting component (for example, titanium oxide or the like) or a reflective resin composition containing a light-reflecting component, and is reflected from the light emitted from the LED 2.

The second sealing layer 12 is filled in the reflector 11, and is specifically formed to cover the inner surface of the reflector 11, the upper surface of the substrate 5 exposed from the LED 2, and the upper surface and the outer surface of the LED 2.

Further, the upper surface of the second sealing layer 12 is formed to form the same plane as the surface of the reflector 11 in the plane direction (the direction orthogonal to the thickness direction). Further, although not shown, a concave portion (not shown) that is gradually recessed from the peripheral end portion toward the central portion may be formed on the upper surface of the second sealing layer 12.

When the fluorescent adhesive sheet 6 is adhered to the LED package 10, as shown in FIG. 8(a), respectively The fluorescent adhesive sheet 6 and the LED package 10 are prepared.

Then, when the polyoxygen adhesive layer 4 is formed of a polyfluorene pressure-sensitive adhesive composition, as shown in FIG. 8(b), the fire is carried out at normal temperature (specifically, 20 to 25 ° C). The optical adhesive sheet 6 is adhered to the upper surface of the LED package 10. Alternatively, the fluorescent adhesive sheet 6 may be heated to, for example, 30 to 50 ° C for adhesion.

On the other hand, when the polyoxygen adhesive layer 4 is formed of a polyoxyxene thermoplastic-thermosetting adhesive composition, the LED package 10 is previously heated, and then the polyoxygen adhesive layer 4 is formed. It is placed on the upper surface of the LED package 10. Thereby, a film 4' of a polyoxyxene thermoplastic-thermosetting adhesive composition is formed on the entire upper surface of the LED package 10.

Thereafter, the LED package 10 is placed on the upper surface of a stage (not shown) at room temperature (20 to 25 ° C), and the polyoxyxene thermoplastic thermosetting adhesive composition is cooled and solidified.

Thereby, the LED device 7 including the LED package 10 on the upper surface via the polyoxygen adhesive layer 4 followed by the phosphor layer 3 can be manufactured.

Further, in the LED device 7, the polyether oxide adhesive composition for adhering the phosphor layer 3 to the LED package 10 has a peel strength of 30% or more, and therefore has excellent heat resistance and durability. . As a result, the LED device 7 can ensure excellent light-emitting reliability for a long period of time.

Further, in the embodiment of Fig. 8, as shown in Fig. 8(a), first, a polyoxygen adhesive layer 4 is laminated on the phosphor layer 3 to form a fluorescent adhesive sheet 6, and thereafter, as shown in Fig. 8 ( As shown in b), the phosphor layer 3 of the fluorescent adhesive sheet 6 is bonded to the LED package 10 via the polyoxygen adhesive layer 4. On the other hand, for example, as shown in FIG. 9(a), first, the surface of the LED package 10 is layered on the surface of the epoxy resin adhesive layer 4, and thereafter, as shown in FIG. 9(b), adhered via polyoxymethylene. The agent layer 4 bonds the phosphor layer 3 to the LED package 10.

In this method, the LED package 10 is first prepared.

Then, in this method, as shown in the lower side view of FIG. 9(a), the surface of the LED package 10 is layered on the surface of the LED package 10.

Specifically, when the polyfluorene pressure-sensitive adhesive composition is prepared as a varnish, the varnish is applied or dropped on the entire upper surface of the LED 2. Thereby, a film of the polyfluorene pressure-sensitive adhesive composition is formed. The solvent in the varnish is then distilled off as needed.

On the other hand, when the polyoxyxylene adhesive composition is formed of a polyoxyxene thermoplastic-thermosetting adhesive composition, the LED package 10 is heated in advance, and then the polyoxynitride molded body 9 is used (refer to The imaginary line of FIG. 2(a) is placed on the upper surface of the LED package 10. Thereby, a film 4' of a polyoxyxene thermoplastic-thermosetting adhesive composition is formed on the entire upper surface of the LED package 10.

Thereafter, as shown in FIG. 9(b), the phosphor layer 3 is bonded to the LED package 10 via the polyoxygen adhesive layer 4. Specifically, the lower surface of the phosphor layer 3 is brought into contact with the upper surface of the polyadox adhesive layer 4.

According to the embodiment of Fig. 9, the same operational effects as those of the embodiment of Fig. 8 can be exhibited.

Further, in the embodiment of FIGS. 1 to 9, the LED 2 is described as the optical semiconductor device of the present invention, but for example, an LD (Laser Diode) 2 may be employed.

In this case, the LED device 7 is set as the laser diode irradiation device 7, and the LED-phosphor layer contact body 1 is used as the LD-phosphor layer bonding body 1, and the LED package 10 is provided. Set to LD package.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Production Examples, Preparation Examples, Comparative Preparation Examples, Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

(production of phosphor ceramic plate) Production example 1

Preparation of cerium oxide particles (purity: 99.99%, lot (batch): N-YT4CP, manufactured by Nippon Yttrium Co., Ltd.) 11.34 g, alumina particles (purity: 99.99%, product number "AKP-30", manufactured by Sumitomo Chemical Co., Ltd.) 8.577 g, and cerium oxide particles 0.087g Raw material powder of phosphor.

20 g of the raw material powder of the prepared phosphor was mixed with a water-soluble binder resin ("WB4101", manufactured by Polymer Inovations, Inc.) so that the volume ratio of the solid content was 60:40, and distilled water was added thereto. In a container made of alumina, a yttria-stabilized zirconia ball having a diameter of 3 mm was added, and wet-mixing was carried out for 24 hours by a ball mill to prepare a slurry solution of raw material particles of the phosphor.

Then, the prepared slurry solution is subjected to belt casting on a PET (polyethylene terephthalate) film by a doctor blade method, and dried at 70 ° C to form a ceramic green sheet. Thereafter, the ceramic green sheet was peeled off from the PET film to obtain a ceramic green sheet having a thickness of 90 μm.

Thereafter, the obtained green sheet was cut into a size of 20 mm × 20 mm, and two sheets were produced and superposed, and heat-laminated using a biaxial hot press, thereby producing a ceramic green sheet. Laminated body.

Thereafter, the produced ceramic green sheet laminate was heated to 1,200 ° C at a temperature elevation rate of 1 ° C/min in an atmosphere by an electric oven (Electric Muffle Furnace) to decompose and remove an organic component such as a binder resin. Adhesive treatment. Thereafter, the laminate is transferred to a high-temperature vacuum furnace, heated to a temperature of 5 ° C / min at a temperature increase rate of about 10 ^-3 Torr (133 × 10 ^-3 N / m ² ) to 1750 ° C, and After calcination at this temperature for 5 hours, a phosphor ceramic plate (phosphor layer) having a thickness of 150 μm was produced.

(Production of phosphor resin sheet) Production example 2

By using an applicator, the YAG phosphor powder (commercial number BYW01A, average particle diameter: 9 μm, manufactured by Phosphor Tech Co., Ltd.) was dispersed on the glass plate so that the concentration of the YAG phosphor powder was 25% by mass. A solution of a thermosetting polyxanthene elastomer (manufactured by Shin-Etsu Silicones Co., Ltd., product number KER2500) to form a phosphor film having a thickness of 150 μm, and heating the phosphor film at 100 ° C for 1 hour. Then, it was heated at 150 ° C for 1 hour to prepare a C-stage phosphor resin sheet (phosphor layer) having a thickness of 150 μm.

(Preparation of polyfluorene pressure-sensitive adhesive composition) Preparation example 1

A polyoxygen pressure-sensitive adhesive composition (trade name: PSA 600, manufactured by General Electronics Co., Ltd.) was prepared.

Further, the raw materials of the polyoxygen peroxide pressure-sensitive adhesive composition are as follows.

. Polydimethyloxane with decyl alcohol groups at both ends

. Octamethylcyclotetraoxane (in the formula (B), R ^a is a methyl group, m is 3) 1 to 5 mass% (relative to the total solid content)

. a mixture of benzamidine-based peroxides (mixtures of benzamidine peroxide, benzammonium peroxide, methylene benzamidine, and toluene toluene)

. Toluene is 45 mass% relative to solid content

(Synthesis of cage-type sesquioxaxane) Synthesis Example 1

To a mixture of 66.8 mL (158.6 mol) of hydrogen tetramethylammonium (25% methanol solution), 32.8 mL of methanol and 24.6 mL of distilled water, 35.8 mL (160.6 mol) of tetraethoxy decane was slowly added dropwise, and stirred for a day and night. Thereby, the reaction is carried out.

Then, the reaction liquid was filtered, and the filtrate was added to a mixture of 428 mL of hexane, 7.1 g (75 mmol) of dimethylchloromethane and 24.4 g (225 mmol) of trimethylchloromethane, and stirred for a day and night. Thereafter, the reactant was extracted with hexane, and magnesium sulfate was added to the extract and dried. Thereafter, after hexane was temporarily removed, hexane was further added thereto to recrystallize, thereby obtaining a cage-type sesquioxaxane having a white solid.

Using ¹ H-NMR confirmed that the structure of cage octasilsesquioxane silicon alumoxane is obtained by the formula (7), the acknowledgment of the formula and (7) R ⁶ is methyl, R ⁷ is hydrogen and methyl, R ⁷ is calculated The molar ratio of methyl group to hydrogen (the average of the cage-type sesquioxaxane as a whole), and the result is methyl: hydrogen = 6:2.

(Preparation of polyoxyl thermoplastic-thermosetting adhesive composition) Preparation example 2

The cage type sesquioxaxane of Synthesis Example 1 (R ⁷ /methyl group of the formula (7): hydrogen (mole ratio) = 6:2) 0.3 g, and polyoxyalkylene containing alkenyl groups at both terminals ( In the formula (8), R ⁸ is a methyl group, R ⁹ is a vinyl group, i is 8, and the number average molecular weight is 800, manufactured by Gelest Corporation, 0.24 g, toluene 1 g, and platinum-divinyl decane are misaligned. The solution (hydrogenated catalyst, toluene solution, platinum concentration: 2% by mass) was mixed at 0.5 μL, and stirred at 50 ° C for 15 hours. The molar ratio (=vinyl/hydroalkylene) of the vinyl group of the alkenyl group-containing polyoxyalkylene to the hydrocarbyl group of the cage octadequioxane was 0.91.

Thereafter, toluene was distilled off, whereby a third polyfluorene-oxygen thermoplastic-thermosetting adhesive composition in the form of a transparent solid was obtained.

Preparation Example 3

The two-terminal amine-based polyoxyxylene resin composition under nitrogen (at 25 ° C) (wherein R ¹ in the formula (1) is all methyl, R ³ is a propyl group and a = 150, b 5 g (0.43 mmol) of a compound represented by =0, a weight average molecular weight of 11,400, manufactured by Shin-Etsu Chemical Co., Ltd., 0.074 g (0.43 mmol) of toluene 2,4-diisocyanate, and 10 mL of methyl ethyl ketone were stirred and mixed for 1 hour. Thereafter, 1315 μL of di-t-butylperoxide (0.1 mol/L benzene solution, manufactured by Nippon Oil & Fats Co., Ltd.) was added (100 mol% based on R ¹ groups of the both-end amine-based polyoxyxylene resin composition, free radical generation) The agent was 0.1 mol%), and the mixture was stirred and stirred at room temperature (25 ° C) for 1 hour. Thereafter, the solvent was removed under reduced pressure at room temperature (25 ° C) to obtain a first polyfluorinated thermoplastic-thermosetting adhesive composition in the form of a transparent solid.

(Preparation of polyoxygenated adhesive composition) Comparison preparation example 1

A polyoxygen pressure-sensitive adhesive composition (trade name, SD 4580 PSA, manufactured by Toray Dow Corning Co., Ltd.) was prepared.

Further, the raw materials of the polyoxygen peroxide pressure-sensitive adhesive composition are as follows.

. Polydimethyloxane with decyl alcohol groups at both ends

. a mixture of benzamidine-based peroxides (mixtures of benzamidine peroxide, benzammonium peroxide, methylene benzamidine, and toluene toluene)

. Toluene is 70% by mass relative to solid content

(Preparation of acrylic pressure-sensitive adhesive composition) Comparison preparation example 2

An acrylic pressure-sensitive adhesive was prepared in accordance with the formulation of Example 2 of JP-A-6-172729.

(Production of optical semiconductor package) Production example 3

A metal core substrate on which a conductor pattern is formed on a laminated substrate in which an insulating layer is laminated on a metal substrate. Then, an optical semiconductor element (blue LED, product number C450EZ1000-0123, manufactured by Cree Co., Ltd.) was attached to the metal core substrate by wire bonding (see the lower side view of FIG. 6(a)).

Production example 4

A substrate is prepared in which a reflector having a substantially elliptical recess (cavity) is laminated on a substrate, and a multilayer ceramic substrate having a conductor pattern formed on a substrate in the recess (Product No. 207806, manufactured by Sumitomo Metal Electronics Devices Co., Ltd.) ).

Then, an optical semiconductor element (blue LED, product number C450EZ1000-0123, manufactured by Cree Co., Ltd.) was bonded to the multilayer ceramic substrate by wire bonding.

Then, a two-liquid mixing type thermosetting polyxanthene elastomer (product number KER2500, manufactured by Shin-Etsu Silicones Co., Ltd.) was poured into the cavity, and then heated at 100 ° C for 1 hour and heated at 150 ° C. Hours, thereby hardening it.

Thereby, a sealing layer is formed (refer to the lower side view of FIG. 8 (a)).

Thereby, an optical semiconductor package is produced.

(production of fluorescent paste) Example 1-a

The phosphor ceramic plate of Production Example 1 was cut into a specific size (3.5 mm × 2.8 mm or 1 mm × 1 mm. Further, in the case of application to the optical semiconductor package of Production Example 3, the bonding wire bonding was also performed. The slit was formed at the position (see Fig. 2 (a)), and thereafter, the polyfluorene pressure-sensitive adhesive composition of Preparation Example 1 was applied to the entire upper surface of the phosphor ceramic plate to form a film. Then, the solvent was distilled off.

Thereby, a polyfluorene pressure-sensitive adhesive layer having a thickness of 40 μm was formed on the upper surface of the phosphor ceramic plate (see FIG. 2(b)). That is, a fluorescent adhesive sheet comprising a phosphor ceramic plate and a polyfluorene pressure-sensitive adhesive layer was produced.

(Manufacture of optical semiconductor device / no cavity) Example 1-b

The phosphor layer in the 1 mm × 1 mm fluorescent adhesive sheet of Example 1-a was bonded to the optical semiconductor element mounted on the substrate of Production Example 3 via a polysilicon oxide pressure-sensitive adhesive layer at 25 ° C. Above the surface.

Thereby, an optical semiconductor device is manufactured (refer FIG. 6 (b)).

(Manufacture of optical semiconductor device / cavity) Example 1-c

The phosphor layer in the 3.5 mm × 2.8 mm fluorescent adhesive sheet of Example 1-a was bonded to the optical semiconductor package of Production Example 4 via a polysilicon oxide pressure-sensitive adhesive layer at 25 ° C. surface.

Thereby, an optical semiconductor device is manufactured (refer FIG. 8 (b)).

(production of fluorescent paste) Example 2-a

In the same manner as in Example 1-a, a phosphor paste sheet of Production Example 2 (see FIG. 2(a)) was used instead of the phosphor ceramic sheet of Production Example 1 to prepare a fluorescent paste. Sheet (refer to Figure 2 (b)).

(Manufacture of optical semiconductor device / no cavity) Example 2-b

The same procedure as in Example 1-b was carried out to produce light by using the fluorescent adhesive sheet of Example 2-a (see FIG. 2(b)) instead of the fluorescent adhesive sheet of Example 1-a. Semiconductor device (see Fig. 6(b)).

(Manufacture of optical semiconductor device / cavity) Example 2-c

The same procedure as in Example 1-c was carried out except that the fluorescent adhesive sheet of Example 2-a (see FIG. 2(b)) was used instead of the fluorescent adhesive sheet of Example 1-a to produce light. Semiconductor device (see Fig. 8(b)).

(Manufacture of fluorescent adhesive sheets) Example 3-a

The phosphor ceramic plate of Production Example 1 was cut into a specific size (size: 3.5 mm × 2.8 mm or 1 mm × 1 mm. Further, in the case of application to the optical semiconductor package of Production Example 3, the bonding wire was also aligned. A slit is formed at the joint position, and it is placed on a hot plate heated to 100 ° C (refer to the solid line of Fig. 2 (a)).

Then, 1 mg of the polyoxymethylene molded article containing the third polyoxyxene thermoplastic thermosetting adhesive composition of Preparation Example 2 was placed on the center of the upper surface of the phosphor ceramic plate (see Fig. 2 (a) line).

In this manner, immediately after the mounting, the polysiloxane molded body is plasticized (liquid) and uniformly diffused on the entire upper surface of the phosphor ceramic plate to form a film of the polyoxyxene thermoplastic-thermosetting adhesive composition (see The imaginary line arrow of Fig. 2(a) and Fig. 2(b)).

Thereafter, the phosphor ceramic plate was taken out from the hot plate and cooled to room temperature. Thereby, the third polyoxyl thermoplastic-thermosetting adhesive composition is solidified.

Thereby, a fluorescent adhesive sheet having a polyoxyxene thermoplastic thermosetting adhesive layer having a thickness of about 100 μm formed on the phosphor layer containing the phosphor ceramic plate was obtained (see FIG. 2(b)).

(Manufacture of optical semiconductor device / no cavity) Example 3-b

In the embodiment 3-a, the following is prepared by heating a phosphor ceramic plate (ceramic plate before cooling, size 1 mm × 1 mm) which is plasticized with a polycrystalline oxide molded body by using a hot plate, and using a hot plate. The substrate of Production Example 3 and the optical semiconductor element mounted thereon (see FIG. 6(a) lower side view) were heated, and it was confirmed that both of them were at the same temperature, and the plasticized polyoxynitride molded body was used for the optical semiconductor element. The upper surface is attached to the phosphor ceramic plate. Thereafter, it was taken out from the hot plate and cooled to room temperature. Thereby, an optical semiconductor device is manufactured (refer FIG. 6 (b)).

(Manufacture of optical semiconductor device / cavity) Example 3-c

The substrate and the optical semiconductor element of Example 3-b were used instead of the optical semiconductor package of Production Example 4 (see the lower side view of Fig. 8(a)), and further, the plasticized size of the polyoxynitride molded body was 3.5 mm × A photo-semiconductor device was fabricated in the same manner as in Example 3-b except that a 2.8 mm phosphor ceramic plate was used (see FIG. 8(b)).

(production of fluorescent paste) Example 4-a

A phosphor paste sheet was obtained in the same manner as in Example 3-a except that the phosphor resin sheet of Production Example 2 was used instead of the phosphor ceramic sheet of Production Example 1 (see FIG. 2(b). ).

(Manufacture of optical semiconductor device / no cavity) Example 4-b

An optical semiconductor device was fabricated in the same manner as in Example 3-b except that the fluorescent adhesive sheet of Example 4-a was used instead of the fluorescent adhesive sheet of Example 3-a (see FIG. 6(b). )).

(Manufacture of optical semiconductor device / cavity) Example 4-c

An optical semiconductor device was manufactured in the same manner as in Example 3-c except that the fluorescent adhesive sheet of Example 4-a was used instead of the fluorescent adhesive sheet of Example 3-a (see FIG. 8(b). )).

(Manufacture of fluorescent adhesive sheets) Example 5-a

The phosphor ceramic plate of Production Example 1 was cut into a specific size (3.5 mm × 2.8 mm or 1 mm × 1 mm. Further, in the case of application to the optical semiconductor package of Production Example 3, the bonding wire bonding was also performed. The slit was made at the position, and it was placed on a hot plate heated to 100 ° C (refer to the solid line of Fig. 2 (a)).

Then, 1 mg of the polyoxynitride molded body containing the first polyoxyxene thermoplastic thermosetting adhesive composition of Preparation Example 3 was placed on the center of the upper surface of the phosphor ceramic plate (refer to FIG. 2(a)). Imaginary line).

In this manner, immediately after the mounting, the polysiloxane molded body is plasticized (liquid) and uniformly diffused on the entire upper surface of the phosphor ceramic plate to form a film of the polyoxyxene thermoplastic-thermosetting adhesive composition (see The imaginary line arrow of Fig. 2(a) and Fig. 2(b)).

Thereafter, the phosphor ceramic plate was taken out from the hot plate and cooled to room temperature. Thereby, the first polyoxyl thermoplastic-thermosetting adhesive composition is solidified.

Thereby, a fluorescent adhesive sheet having a polyoxyxene thermoplastic thermosetting adhesive layer having a thickness of about 100 μm formed on the phosphor layer containing the phosphor ceramic plate was obtained (see FIG. 2(b)).

(Manufacture of optical semiconductor device / no cavity) Example 5-b

In the embodiment 5-a, a phosphor ceramic plate (ceramic plate before cooling, size 1 mm × 1 mm) which is plasticized by a hot plate while being heated by a hot plate is used, and is heated by a hot plate. The substrate of Production Example 3 and the optical semiconductor element mounted thereon (see the lower side view of FIG. 6(a)), and it was confirmed that both of them were at the same temperature, and the plasticized polyoxynitride molded body was used in the optical semiconductor element. The upper surface is attached to the phosphor ceramic plate. Thereafter, take it from the hot plate Out and cool to room temperature. Thereby, an optical semiconductor device is manufactured (refer FIG. 6 (b)).

(Manufacture of optical semiconductor device / cavity) Example 5-c

The substrate and the optical semiconductor element of Example 5-b were used instead of the optical semiconductor package of Production Example 4 (see the lower side view of Fig. 8(a)), and further, the plasticized size of the polyoxynitride molded body was 3.5 mm × A photo-semiconductor device was fabricated in the same manner as in Example 5-b except that a 2.8 mm phosphor ceramic plate was used (see FIG. 8(b)).

(production of fluorescent paste) Example 6-a

A phosphor paste sheet was obtained in the same manner as in Example 5-a except that the phosphor resin sheet of Production Example 2 was used instead of the phosphor ceramic sheet of Production Example 1 (see FIG. 2(b). ).

(Manufacture of optical semiconductor device / no cavity) Example 6-b

An optical semiconductor device was produced in the same manner as in Example 5-b except that the fluorescent adhesive sheet of Example 6-a was used instead of the fluorescent adhesive sheet of Example 5-a (see FIG. 6(b). )).

(Manufacture of optical semiconductor device / cavity) Example 6-c

An optical semiconductor device was produced in the same manner as in Example 5-c except that the fluorescent adhesive sheet of Example 6-a was used instead of the fluorescent adhesive sheet of Example 5-a (see FIG. 8(b). )).

(production of fluorescent paste) Comparative Example 1-a

The phosphor ceramic plate of Production Example 1 was cut into a specific size (3.5 mm × 2.8 mm or 1 mm × 1 mm. Further, when applied to the optical semiconductor package of Production Example 3, A slit is also formed at a position where the bonding wire is bonded (see FIG. 2(a)), and thereafter, the polyfluorene pressure-sensitive adhesive composition of Comparative Preparation Example 1 is applied to the entire upper surface of the phosphor ceramic plate. Form a film. Then, the solvent was distilled off.

Thereby, a polyfluorene pressure-sensitive adhesive layer having a thickness of 40 μm was formed on the upper surface of the phosphor ceramic plate (see FIG. 2(b)). That is, a fluorescent adhesive sheet comprising a phosphor ceramic plate and a polyfluorene pressure-sensitive adhesive layer was produced.

(Manufacture of optical semiconductor device / no cavity) Comparative Example 1-b

The phosphor layer in the phosphor paste of the size of 1 mm × 1 mm of Comparative Example 1-a was bonded to the optical semiconductor element mounted on the substrate of Production Example 3 via a polysilicon oxide pressure-sensitive adhesive layer at 25 ° C. Above the surface.

Thereby, an optical semiconductor device is manufactured (refer FIG. 6 (b)).

(Manufacture of optical semiconductor device / cavity) Comparative Example 1-c

The phosphor layer in the 3.5 mm × 2.8 mm fluorescent adhesive sheet of Comparative Example 1-a was bonded to the optical semiconductor package of Production Example 4 via a polysilicon oxide pressure-sensitive adhesive layer at 25 ° C. surface.

Thereby, an optical semiconductor device is manufactured (refer FIG. 8 (b)).

(production of fluorescent paste) Comparative Example 2-a

In the same manner as in Comparative Example 1-a, a phosphor paste sheet of Production Example 2 (see FIG. 2(a)) was used instead of the phosphor ceramic plate of Production Example 1 to prepare a fluorescent paste. Sheet (refer to Figure 2 (b)).

(Manufacture of optical semiconductor device / no cavity) Comparative Example 2-b

The fluorescent patch of Comparative Example 2-a (refer to FIG. 2(b)) was used instead of the fluorescent light of Comparative Example 1-a. Other than the above, the film was processed in the same manner as in Comparative Example 1-b to produce an optical semiconductor device (see FIG. 6(b)).

(Manufacture of optical semiconductor device / cavity) Comparative Example 2-c

The same procedure as in Comparative Example 1-c was used to produce light, except that the fluorescent adhesive sheet of Comparative Example 2-a (see FIG. 2(b)) was used instead of the fluorescent adhesive sheet of Comparative Example 1-a. Semiconductor device (see Fig. 8(b)).

(production of fluorescent paste) Comparative Example 3-a

The phosphor ceramic plate of Production Example 1 was cut into a specific size (3.5 mm × 2.8 mm or 1 mm × 1 mm. Further, in the case of application to the optical semiconductor package of Production Example 3, the bonding wire bonding was also performed. The slit was formed at the position (see Fig. 2 (a)), and thereafter, the acrylic pressure-sensitive adhesive composition of Comparative Preparation Example 2 was applied to the entire upper surface of the phosphor ceramic plate to form a film. Then, the solvent was distilled off.

Thereby, an acrylic pressure-sensitive adhesive layer having a thickness of 40 μm was formed on the upper surface of the phosphor ceramic plate (see FIG. 2(b)). That is, a fluorescent adhesive sheet containing a phosphor ceramic plate and an acrylic pressure-sensitive adhesive layer was produced.

(Manufacture of optical semiconductor device / no cavity) Comparative Example 3-b

The phosphor layer in the phosphor paste of the size of 1 mm × 1 mm of Comparative Example 3-a was bonded to the optical semiconductor element mounted on the substrate of Production Example 3 via an acrylic pressure-sensitive adhesive layer at 25 ° C. Upper surface.

Thereby, an optical semiconductor device is manufactured (refer FIG. 6 (b)).

(Manufacture of optical semiconductor device / cavity) Comparative Example 1-c

In the fluorescent adhesive sheet of Comparative Example 1-a having a size of 3.5 mm × 2.8 mm at 25 ° C The phosphor layer was bonded to the upper surface of the optical semiconductor package of Production Example 4 via an acrylic pressure-sensitive adhesive layer.

Thereby, an optical semiconductor device is manufactured (refer FIG. 8 (b)).

(production of fluorescent paste) Comparative Example 4-a

A phosphor paste was prepared in the same manner as in Comparative Example 3-a except that the phosphor resin sheet of Production Example 2 (see FIG. 2(a)) was used instead of the phosphor ceramic plate of Comparative Example 3 to prepare a fluorescent paste. Sheet (refer to Figure 2 (b)).

(Manufacture of optical semiconductor device / no cavity) Comparative Example 4-b

The light-sensitive adhesive sheet of Comparative Example 4-a (see FIG. 2(b)) was used in the same manner as in Comparative Example 3-b except that the fluorescent adhesive sheet of Comparative Example 3-a was used instead of the above. Semiconductor device (see Fig. 6(b)).

(Manufacture of optical semiconductor device / cavity) Comparative Example 4-c

The same procedure as in Comparative Example 3-c was carried out to produce light using the fluorescent adhesive sheet of Comparative Example 4-a (see FIG. 2(b)) instead of the fluorescent adhesive sheet of Comparative Example 3-a. Semiconductor device (see Fig. 8(b)).

The combination and evaluation results of the materials used for the phosphor layer and the adhesive composition in each of the examples and the comparative examples are shown in Table 1.

(Evaluation)

With respect to each of the adhesive layers (adhesive composition) of the examples and the comparative examples, the peel strength to the phosphor layer was evaluated by the following method.

Moreover, the light-emitting reliability over time of each of the optical semiconductor devices of the examples and the comparative examples was also evaluated. These results are shown in Table 1.

Peel strength

The peel strength of the adhesive layer to the phosphor ceramic plate in each of the environments of 25 ° C and 75 ° C was calculated by a peeling adhesion force [N/19 mm] having a width of 19 mm.

Specifically, the adhesive composition was applied to the surface of the polyimide film having a thickness of 25 μm as a support so as to have a width of 19 mm and a thickness of 40 μm. Thereby, an adhesive layer laminated on the support is formed. Then, the polyimide film having the adhesive layer was pressure-bonded to a phosphor ceramic plate having a size of 20 mm × 20 mm by reciprocating from the upper side of the polyimide film by a 2 kg roller. Leave it for about 30 minutes after crimping. Then, it is installed in a tensile tester (the name of the device: manufactured by Shimadzu Corporation, and the tensile tester AUTOGRAPH AG-10kNX), which is placed in a thermostat set to a specific temperature, and is kept at the following temperature. After 5 minutes, the polyimide film and the adhesive layer were peeled off (peeled off) from the phosphor ceramic plate under the following conditions, and the peeling adhesion force at this time was measured as the peel strength.

Temperature in the thermostat: 25 ° C or 75 ° C

Peeling (peeling) conditions: peeling angle of 180 degrees

Stretching speed 300mm/min

After the measurement, the peel strength PS _{75 ° C} [N/19 mm] at 75 ° C was calculated as a percentage of the peel strength PS _{25 ° C} [N/19 mm] at _{25 ° C} ([PS _{75 ° C} / PS _{25 ° C} ] × 100).

2. Surface temperature of the phosphor layer when the optical semiconductor device is lit

Using a sufficiently sized heat sink and a thermally conductive grease to connect the examples and comparative examples The optical semiconductor device is further electrically connected to the power source. Then, the luminance (initial luminance) at the time of initial light emission of the optical semiconductor device and the luminance at 30 days of continuous light emission (luminance after 30 days) were measured by applying a current of 350 mA from the power source.

Then, the percentage of the luminance with respect to the initial luminance after 30 days ([luminescence after 30 days/initial luminance] × 100) was calculated.

Further, in Comparative Example 1-b to Comparative Example 2-c, since the polyfluorene pressure-sensitive adhesive layer was peeled off from the phosphor ceramic plate, the luminance after 30 days could not be measured, and the above percentage could not be calculated.

In addition, the above description is provided as an exemplified embodiment of the present invention, but it is merely illustrative and not to be construed as limiting. Variations of the invention that are apparent to those skilled in the art are included in the scope of the following claims.

1‧‧‧LED-phosphor layer adhesion

2‧‧‧LED

3‧‧‧Fluorescent layer

4‧‧‧Polyoxygen adhesive layer

Claims (6)

A phosphor layer adhesive kit, comprising: a phosphor layer; and a polyoxygen adhesive composition for adhering the phosphor layer to an optical semiconductor element or an optical semiconductor device package, and the polyfluorene composition The percentage of the following peel strength of the oxygen adhesive composition is 30% or more, and the percentage of peel strength = [(peel strength at _{75 ° C} , PS _{75 ° C} ) / (peel strength at _{25 ° C} , PS _{25 ° C} )] peeling under the × 100 75 ℃ environment strength PS _{75 ℃} lines by the above-described poly silicon oxide adhesion adhesive composition is formed and laminated on the support of the above stick on the body adhesive layer is adhered to said phosphor layer, and thereafter, at a temperature of 75 The peel strength when the support and the adhesive layer are peeled off from the phosphor layer at a peeling angle of 180 degrees and a speed of 300 mm/min at ° C, and the peel strength PS _{25 °} C in an environment of _{25 ° C} will be adhered by the above polyoxyl The adhesive layer formed on the support and laminated on the support is adhered to the phosphor layer, and then the support and the adhesive are adhered at a peeling angle of 180 degrees and a speed of 300 mm/min at a temperature of 25 ° C. Subsequent layer Said peel strength of the phosphor layer peeled. The phosphor layer adhesive kit of claim 1, wherein the polyoxygen oxide adhesive composition is a polyoxygen peroxide pressure adhesive composition. The phosphor layer adhesive kit of claim 1, wherein the polyoxyxylene adhesive composition is a thermoplastic and thermosetting thermoplastic composition having both thermoplasticity and thermosetting properties. An optical semiconductor element-phosphor layer adhesive body, comprising: an optical semiconductor element; and a fluorescent adhesive layer comprising a phosphor layer and a layer for bonding the phosphor layer to the optical semiconductor element a phosphor layer adhesive set of the polyoxygen adhesive composition, wherein the phosphor layer is adhered to the optical semiconductor element via the polyoxygen adhesive composition; and the polyoxygen adhesive The percentage of the following peel strength of the composition is 30% or more, and the percentage of peel strength = [(peel strength at 75 ° C environment PS _{75 ° C} ) / (peel strength _at 25 ° C environment PS _{25 ° C} )] × 100 75 ° C Peeling strength in the environment PS _{75 ° C} is obtained by adhering the above-mentioned adhesive layer formed of the above polyfluorene adhesive composition and laminated on the support to the above-mentioned phosphor layer, and then peeling off at a temperature of 75 ° C angle of 180 degrees, the speed of 300mm / min to the supporting member and said stick is then peeled from the release agent layer strength when said phosphor layer is peeled off, the intensity of the environment 25 deg.] C PS _{25 ℃} silicon oxide-based adhesion by the above adhesive polyethylene compositions The adhesive layer formed on the support and adhered to the phosphor layer is adhered to the phosphor layer, and then the support and the adhesive layer are formed at a peeling angle of 180 degrees and a speed of 300 mm/min at a temperature of 25 ° C. The peel strength at the time of peeling of the above-mentioned phosphor layer. An optical semiconductor device, comprising: a substrate; an optical semiconductor component mounted on the substrate; and a fluorescent adhesive layer comprising a phosphor layer and bonding the phosphor layer to the optical semiconductor component a phosphor layer adhesive set of the above polyoxygen adhesive composition, wherein the phosphor layer is adhered to the optical semiconductor element via the polyoxygen adhesive composition; and the polyoxygen oxide is adhered The percentage of the following peel strength of the subsequent composition is 30% or more, and the percentage of peel strength = [(peel strength at _{75 ° C} , PS _{75 ° C} ) / (peel strength at _{25 ° C} , PS _{25 ° C} )] × 100 Peel strength at _{75 ° C.} PS _{75 ° C} is a layer of the adhesive layer formed of the above polyadox adhesive composition and laminated on a support, and then adhered to the above-mentioned phosphor layer, and then at a temperature of 75 ° C The peeling strength when the support and the adhesive layer are peeled off from the phosphor layer at a peeling angle of 180 degrees and a speed of 300 mm/min, and the peel strength PS _{25 °} C in an environment of _{25 ° C} will be bonded by the above-mentioned polyfluorene oxide. The adhesive layer formed on the support composition and laminated on the support is adhered to the phosphor layer, and then the support and the adhesive are adhered at a peeling angle of 180 degrees and a speed of 300 mm/min at a temperature of 25 ° C. The peel strength of the subsequent layer when peeling off from the above phosphor layer. An optical semiconductor device comprising: a substrate; an optical semiconductor element mounted on the substrate; and an optical semiconductor element formed on the substrate in a thickness direction thereof and surrounding the substrate in a thickness direction a reflector disposed in the form of an optical semiconductor element; and a sealing layer filled in the reflector to seal the optical semiconductor element; and a fluorescent adhesive layer comprising a phosphor layer and a layer for bonding the phosphor layer a phosphor layer adhesive set of the polyoxynitride adhesive composition on the optical semiconductor device package, wherein the phosphor layer is adhered to the optical semiconductor package via the polyoxygen adhesive composition The thickness direction side is the same; and the polyether oxide adhesive composition has a percentage of the following peel strength of 30% or more, and the percentage of peel strength = [(peel strength at 75 ° C environment PS _{75 ° C} ) / (25 Peel strength under °C environment PS _25°C )]×100 Peel strength at 75°C environment PS _75°C will be formed from the above polyfluorene adhesive composition and laminated The adhesive layer on the support is adhered to the phosphor layer, and then the support and the adhesive layer are irradiated from the fluorescent layer at a peeling angle of 180 degrees and a speed of 300 mm/min at a temperature of 75 ° C. Peel strength at the time of peeling of the body layer, peel strength in an environment of _{25 ° C} , PS _{25 ° C} , the above-mentioned adhesive layer formed of the above-mentioned polyoxynoxy adhesive composition and laminated on the support is adhered to the above-mentioned phosphor layer. Thereafter, the peel strength of the support and the adhesive layer from the phosphor layer was peeled at a peeling angle of 180 degrees and a speed of 300 mm/min at a temperature of 25 °C.